US20230028401A1 - Nonaqueous electrolyte energy storage device and method for manufacturing the same - Google Patents
Nonaqueous electrolyte energy storage device and method for manufacturing the same Download PDFInfo
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- US20230028401A1 US20230028401A1 US17/784,803 US202017784803A US2023028401A1 US 20230028401 A1 US20230028401 A1 US 20230028401A1 US 202017784803 A US202017784803 A US 202017784803A US 2023028401 A1 US2023028401 A1 US 2023028401A1
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- United States
- Prior art keywords
- lithium
- nonaqueous electrolyte
- energy storage
- silver
- storage device
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 196
- 238000004146 energy storage Methods 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 111
- 229910052709 silver Inorganic materials 0.000 claims abstract description 95
- 239000004332 silver Substances 0.000 claims abstract description 95
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 92
- 239000001989 lithium alloy Substances 0.000 claims abstract description 92
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000002904 solvent Substances 0.000 claims abstract description 56
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 34
- 239000011737 fluorine Substances 0.000 claims abstract description 32
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 32
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 32
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 35
- -1 lithium transition metal Chemical class 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 239000002905 metal composite material Substances 0.000 claims description 21
- 239000011572 manganese Substances 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 16
- 150000003624 transition metals Chemical class 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 75
- 239000010410 layer Substances 0.000 description 44
- 229910052751 metal Inorganic materials 0.000 description 38
- 239000002184 metal Substances 0.000 description 38
- 239000007774 positive electrode material Substances 0.000 description 37
- 239000000758 substrate Substances 0.000 description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 29
- 239000007773 negative electrode material Substances 0.000 description 25
- 210000001787 dendrite Anatomy 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 13
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- 239000011230 binding agent Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- WUALQPNAHOKFBR-UHFFFAOYSA-N lithium silver Chemical compound [Li].[Ag] WUALQPNAHOKFBR-UHFFFAOYSA-N 0.000 description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 7
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
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- 229910000578 Li2CoPO4F Inorganic materials 0.000 description 1
- 229910010142 Li2MnSiO4 Inorganic materials 0.000 description 1
- 229910001367 Li3V2(PO4)3 Inorganic materials 0.000 description 1
- 229910013375 LiC Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013392 LiN(SO2CF3)(SO2C4F9) Inorganic materials 0.000 description 1
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 description 1
- 229910013426 LiN(SO2F)2 Inorganic materials 0.000 description 1
- 229910013084 LiNiPO4 Inorganic materials 0.000 description 1
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
- 229910015329 LixMn2O4 Inorganic materials 0.000 description 1
- 229910008445 Li—Ag Inorganic materials 0.000 description 1
- 229910008447 Li—Al Inorganic materials 0.000 description 1
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- 229910007049 Li—Zn Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
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- WLLOZRDOFANZMZ-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) carbonate Chemical compound FC(F)(F)COC(=O)OCC(F)(F)F WLLOZRDOFANZMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
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- 238000007865 diluting Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
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- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
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- PMGBATZKLCISOD-UHFFFAOYSA-N methyl 3,3,3-trifluoropropanoate Chemical compound COC(=O)CC(F)(F)F PMGBATZKLCISOD-UHFFFAOYSA-N 0.000 description 1
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- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- ZDCRNXMZSKCKRF-UHFFFAOYSA-N tert-butyl 4-(4-bromoanilino)piperidine-1-carboxylate Chemical compound C1CN(C(=O)OC(C)(C)C)CCC1NC1=CC=C(Br)C=C1 ZDCRNXMZSKCKRF-UHFFFAOYSA-N 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- ZMQDTYVODWKHNT-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) phosphate Chemical compound FC(F)(F)COP(=O)(OCC(F)(F)F)OCC(F)(F)F ZMQDTYVODWKHNT-UHFFFAOYSA-N 0.000 description 1
- BWKQKTMHHAZKLV-UHFFFAOYSA-N tris(2,2-difluoroethyl) phosphate Chemical compound FC(F)COP(=O)(OCC(F)F)OCC(F)F BWKQKTMHHAZKLV-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a nonaqueous electrolyte energy storage device and a method for manufacturing the same.
- Nonaqueous electrolyte secondary batteries typified by lithium ion secondary batteries are widely used for electronic devices such as personal computers and communication terminals, motor vehicles, and the like since these secondary batteries have a high energy density.
- the nonaqueous electrolyte secondary batteries generally include a pair of electrodes, which are electrically separated from each other by a separator, and a nonaqueous electrolyte interposed between the electrodes, and are configured to allow ions to be transferred between the two electrodes for charge-discharge.
- Capacitors such as lithium ion capacitors and electric double-layer capacitors are also widely used as nonaqueous electrolyte energy storage devices other than nonaqueous electrolyte secondary batteries.
- Metal lithium is known as a negative active material with a high energy density for use in nonaqueous electrolyte energy storage devices.
- metal lithium may be precipitated in a dendritic form at the surface of the negative electrode during charge (hereinafter, metal lithium in a dendritic form is referred to as a “dendrite”).
- a dendrite metal lithium in a dendritic form
- a nonaqueous electrolyte energy storage device including metal lithium as a negative active material has the disadvantage that a short circuit is likely to be caused by repeating charge-discharge.
- Patent Documents 1 to 3 As a technique for suppressing the growth of the dendrite, the use of a lithium alloy for a negative active material has been proposed (see Patent Documents 1 to 3).
- Patent Document 1 describes the invention of a nonaqueous electrolyte solution secondary battery characterized in that a negative electrode is an alloy in solid solution of; lithium; and a metal capable of dissolution in lithium as a solid solution.
- a negative electrode is an alloy in solid solution of; lithium; and a metal capable of dissolution in lithium as a solid solution.
- zinc, magnesium, and silver are used as a metal capable of dissolution in lithium as a solid solution, with the result that charge-discharge cycle characteristics are similarly improved in each case of the lithium alloys used.
- a mixed solvent of propylene carbonate and 1,2-dimethoxyethane that are equal in volume is used as a nonaqueous solvent.
- a nonaqueous electrolyte solution with a lithium perchlorate dissolved in the mixed solvent of propylene carbonate and 1,2-dimethoxyethane that are equal in volume is used as a nonaqueous electrolyte.
- nonaqueous electrolyte energy storage devices the use of fluorinated solvents such as fluorinated carbonates have been studied for purpose such as suppressing the oxidative decomposition of nonaqueous electrolytes, caused under high potentials.
- the inventors have found, however, that in the case of a nonaqueous electrolyte energy storage device in which a nonaqueous electrolyte containing a fluorinated solvent is used, short circuits may be inadequately suppressed even by simply using, as a negative active material, an alloy of a metal capable of dissolution in lithium as a solid solution and metal lithium as mentioned in Patent Document 1.
- nonaqueous electrolyte energy storage devices typically, fluorine-containing lithium salts with favorable oxidation resistance, solubility, dissociability of lithium ions, and the like are often used as the electrolyte salt.
- the inventors have found, however, that in the case of a nonaqueous electrolyte energy storage device in which a nonaqueous electrolyte including a lithium salt containing fluorine is used, short circuits may be inadequately suppressed even by simply using, as a negative active material, an alloy of a metal capable of dissolution in lithium as a solid solution and metal lithium as mentioned in Patent Document 1.
- the present invention has been made in view of the circumstances as described above.
- An object of the present invention is to provide a nonaqueous electrolyte energy storage device including a nonaqueous electrolyte containing a fluorinated solvent, in which any short circuit is suppressed, and a method for manufacturing such a nonaqueous electrolyte energy storage device.
- Another object of the present invention is to provide a nonaqueous electrolyte energy storage device including a nonaqueous electrolyte including a lithium salt containing fluorine, in which any short circuit is suppressed, and a method for manufacturing such a nonaqueous electrolyte energy storage device.
- An aspect of the present invention is a nonaqueous electrolyte energy storage device that includes a negative electrode including a lithium alloy and a nonaqueous electrolyte containing a fluorinated solvent, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- Another aspect of the present invention is a nonaqueous electrolyte energy storage device that includes a negative electrode including a lithium alloy and a nonaqueous electrolyte including a lithium salt containing fluorine, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- Another aspect of the present invention is a method for manufacturing a nonaqueous electrolyte energy storage device, including: preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte containing a fluorinated solvent, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- Another aspect of the present invention is a method for manufacturing a nonaqueous electrolyte energy storage device, including: preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte including a lithium salt containing fluorine, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- a nonaqueous electrolyte energy storage device including a nonaqueous electrolyte containing a fluorinated solvent, in which any short circuit is suppressed, and a method for manufacturing such a nonaqueous electrolyte energy storage device.
- nonaqueous electrolyte energy storage device including a nonaqueous electrolyte including a lithium salt containing fluorine, in which any short circuit is suppressed, and a method for manufacturing such a nonaqueous electrolyte energy storage device.
- FIG. 1 is an external perspective view showing a nonaqueous electrolyte energy storage device according to one embodiment of the present invention.
- FIG. 2 is a schematic view illustrating an energy storage apparatus configured by assembling a plurality of the nonaqueous electrolyte energy storage devices according to an embodiment of the present invention.
- FIG. 3 is a graph showing the number of cycles until causing any short circuit in nonaqueous electrolyte energy storage devices according to examples and comparative examples.
- FIG. 4 is a graph showing an amount of charge for each cycle in a charge-discharge cycle test for a nonaqueous electrolyte energy storage device according to Example 1.
- FIG. 5 shows the charge-discharge curves of nonaqueous electrolyte energy storage devices according to Example 1 and Comparative Example 11 in the first cycle.
- a nonaqueous electrolyte energy storage device is a nonaqueous electrolyte energy storage device that includes a negative electrode including a lithium alloy and a nonaqueous electrolyte containing a fluorinated solvent, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- the nonaqueous electrolyte energy storage device suppresses, in spite of including the nonaqueous electrolyte containing the fluorinated solvent, a short circuit due to the growth of a dendrite. Although the reason for this is not clear, the following reason is presumed.
- the paragraphs [0008], [0020], and the like of Patent Document 1 describes that the solid solution of a metal in lithium changes the crystal structure of the lithium to cause many active sites for precipitation to be present, thereby densely precipitating lithium during charge, and then inhibiting any dendritic growth. Based on such a theory, the same effect is considered also produced without being affected by the type of the metal in the solid solution in lithium and the type of the nonaqueous solvent.
- Patent Document 1 no difference in the effect due to the metal species in the solid solution is found in any example of Patent Document 1.
- a film containing LiF formed on the surface of the negative electrode This film, which is derived from a fluorinated solvent or the like, acts for inhibiting the dendrite growth, but when a lithium alloy is used for the negative electrode, the film formed on the surface of the negative electrode is considered likely to be inhomogeneous in some cases, depending on the type of the lithium alloy.
- metal lithium is likely to be precipitated on the inhomogeneous part of the film, and thus, depending on charge-discharge conditions or the like, the dendrite growth is presumed to be unlikely to be sufficiently inhibited.
- the lithium alloy for use in the negative electrode contains silver, and when the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less, possibly because no oxidative-reductive reaction of the silver is substantially developed during charge-discharge, a film derived from the fluorinated solvent or the like, formed on the surface of the negative electrode, is likely to have high homogeneity, and the dendrite growth is presumed to be sufficiently suppressed, thereby making any short circuit unlikely to be caused.
- the nonaqueous electrolyte energy storage device has a sufficiently high energy density, because the content of silver with respect to the total content of lithium and silver in the lithium alloy is 20% by mass or less, with the high content of lithium. Furthermore, the nonaqueous electrolyte energy storage device, in which the dendrite growth is inhibited, thus allows sufficient discharge with a small decrease in charge-discharge efficiency.
- a nonaqueous electrolyte energy storage device is a nonaqueous electrolyte energy storage device that includes a negative electrode including a lithium alloy and a nonaqueous electrolyte including a lithium salt containing fluorine, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- the nonaqueous electrolyte energy storage device suppresses, in spite of including the nonaqueous electrolyte including the lithium salt containing fluorine, a short circuit due to the growth of a dendrite. Although the reason for this is not clear, the following reason is presumed.
- the paragraphs [0008], [0020], and the like of Patent Document 1 describes that the solid solution of a metal in lithium changes the crystal structure of the lithium to cause many active sites for precipitation to be present, thereby densely precipitating lithium during charge, and then inhibiting any dendritic growth. Based on such a theory, the same effect is considered also produced without being affected by the type of the metal in the solid solution in lithium and the type of the electrolyte salt.
- Patent Document 1 no difference in the effect due to the metal species in the solid solution is found in any example of Patent Document 1.
- a film containing LiF formed on the surface of the negative electrode This film, which is derived from a lithium salt containing fluorine, or the like, acts for inhibiting the dendrite growth, but when a lithium alloy is used for the negative electrode, the film formed on the surface of the negative electrode is considered likely to be inhomogeneous in some cases, depending on the type of the lithium alloy.
- metal lithium is likely to be precipitated on the inhomogeneous part of the film, and thus, depending on charge-discharge conditions or the like, the dendrite growth is presumed to be unlikely to be sufficiently inhibited.
- the lithium alloy for use in the negative electrode contains silver, and when the content of silver in the lithium alloy is 3% by mass or more and 20% by mass or less, possibly because no oxidative-reductive reaction of the silver is substantially developed during charge-discharge, a film derived from the lithium salt containing fluorine, or the like, formed on the surface of the negative electrode, is likely to have high homogeneity, and the dendrite growth is presumed to be sufficiently suppressed, thereby making any short circuit unlikely to be caused.
- the nonaqueous electrolyte energy storage device has a sufficiently high energy density, because the content of silver in the lithium alloy is 20% by mass or less, with the high content of lithium. Furthermore, the nonaqueous electrolyte energy storage device, in which the dendrite growth is inhibited, thus allows sufficient discharge with a small decrease in charge-discharge efficiency.
- the composition ratio of atoms constituting the lithium alloy (negative active material) in the negative electrode refers to a composition ratio in the lithium alloy discharged by the following method.
- the nonaqueous electrolyte energy storage device is subjected to constant current charge with a current of 0.05 C until the voltage becomes an end-of-charge voltage under normal usage, so that the energy storage device is brought to a fully charged state.
- the nonaqueous electrolyte energy storage device is subjected to constant current discharge with a current of 0.05 C to the lower limit voltage during normal usage.
- the nonaqueous electrolyte energy storage device is disassembled, and the negative electrode is taken out.
- the lithium alloy is collected from the taken-out negative electrode.
- the term “under normal usage” means use of the nonaqueous electrolyte energy storage device while employing charge conditions recommended or specified for the nonaqueous electrolyte energy storage device.
- the term refers to a case of using the nonaqueous electrolyte energy storage device by applying the charger.
- the positive electrode potential at the end-of-charge voltage under normal usage is preferably 4.30 V vs. Li/Li + or higher.
- the positive electrode potential at the end-of-charge voltage under normal usage is 4.30 V vs. Li/Li + or higher, the nonaqueous electrolyte tends to be easily oxidatively decomposed, and the need for the use of a fluorinated solvent and/or a lithium salt containing fluorine is increased, thus increasing the usefulness of the present invention.
- the positive electrode potential at the end-of-charge voltage under normal usage is 4.30 V vs. Li/Li + or higher, a nonaqueous electrolyte energy storage device with a high energy density can be provided in combination with the use of the lithium alloy as a negative active material.
- the nonaqueous electrolyte energy storage device includes a positive electrode including a lithium transition metal composite oxide, in which the lithium transition metal composite oxide preferably has an ⁇ -NaFeO 2 -type crystal structure, contains nickel or manganese as a transition metal, and has a molar ratio (Li/Me) of lithium (Li) to the transition metal (Me) in excess of 1.
- a lithium transition metal composite oxide is a positive active material that is high in electric capacity, and a nonaqueous electrolyte energy storage device including a positive electrode including the oxide is often used at a high current density.
- the nonaqueous electrolyte energy storage device including the positive electrode including the lithium transition metal composite oxide mentioned above, the effect of suppressing any short circuit can be more remarkably enjoyed.
- the composition ratio of atoms constituting the positive active material refers to a composition ratio in a positive active material subjected to no charge-discharge, or a positive active material completely discharged by the following method.
- the nonaqueous electrolyte energy storage device is subjected to constant current charge with a current of 0.05 C until the voltage becomes an end-of-charge voltage under normal usage, so that the energy storage device is brought to a fully charged state.
- the nonaqueous electrolyte energy storage device is subjected to constant current discharge with a current of 0.05 C to the lower limit voltage during normal usage.
- a test battery using a metal lithium electrode as the counter electrode is assembled, constant current discharge is performed at a current value of 10 mA per 1 g of a positive composite until the positive potential reaches 2.0 V (vs. Li/Li + ), and the positive electrode is adjusted to the completely discharged state.
- the test battery is disassembled, and the positive electrode is taken out. An oxide of the positive active material is collected from the taken-out positive electrode.
- the lithium alloy mentioned above is preferably composed substantially of lithium and silver. Any element other than silver is substantially not contained with respect to metal lithium, thereby allowing discharge at a low negative electrode potential that is equivalent to that for metal lithium, and then allowing a high energy density to be achieved.
- the lithium alloy is composed substantially of lithium and silver, the content ratio of lithium can be increased, and the electric capacity can be increased.
- a method for manufacturing a nonaqueous electrolyte energy storage device is a method for manufacturing a nonaqueous electrolyte energy storage device, including: preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte containing a fluorinated solvent, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- the manufacturing method is capable of manufacturing a nonaqueous electrolyte energy storage device including a nonaqueous electrolyte containing a fluorinated solvent, in which a short circuit is suppressed.
- a method for manufacturing a nonaqueous electrolyte energy storage device is a method for manufacturing a nonaqueous electrolyte energy storage device, including; preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte including a lithium salt containing fluorine, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- the manufacturing method is capable of manufacturing a nonaqueous electrolyte energy storage device including a nonaqueous electrolyte including a lithium salt containing fluorine, in which a short circuit is suppressed.
- nonaqueous electrolyte energy storage device according to an embodiment of the present invention and the method for manufacturing the nonaqueous electrolyte energy storage device will be described in order.
- the nonaqueous electrolyte energy storage device has a positive electrode, a negative electrode, and a nonaqueous electrolyte.
- a nonaqueous electrolyte secondary battery (hereinafter, also simply referred to as a “secondary battery”) will be described as an example of the nonaqueous electrolyte energy storage device.
- the positive electrode and the negative electrode usually form an electrode assembly in which the positive electrode and the negative electrode are alternately superposed by being stacked or wound with a separator interposed therebetween.
- the electrode assembly is housed in a case, and the case is filled with the nonaqueous electrolyte.
- the nonaqueous electrolyte is interposed between the positive electrode and the negative electrode.
- a known metal case, a resin case or the like which is usually used as a case of a secondary battery, can be used.
- the positive electrode has a positive substrate and a positive active material layer disposed directly or via an intermediate layer on the positive substrate.
- the positive substrate has conductivity. Having “conductivity” means having a volume resistivity of 10 7 ⁇ cm or less that is measured in accordance with JIS-H-0505 (1975), and the term “non-conductivity” means that the volume resistivity is more than 10 7 ⁇ cm.
- a metal such as aluminum, titanium, tantalum, stainless steel, or an alloy thereof is used.
- aluminum and aluminum alloys are preferable from the viewpoint of the balance of electric potential resistance, high conductivity, and cost.
- Example of the form of formation of the positive substrate include a foil and a vapor deposition film, and a foil is preferred from the viewpoint of cost. In other words, an aluminum foil is preferable as the positive substrate.
- Examples of the aluminum or aluminum alloy include A1085 and A3003 prescribed in JIS-H-4000 (2014).
- the average thickness of the positive substrate is preferably 3 ⁇ m or more and 50 ⁇ m or less, more preferably 5 ⁇ m or more and 40 ⁇ m or less, still more preferably 8 ⁇ m or more and 30 ⁇ m or less, and particularly preferably 10 ⁇ m or more and 25 ⁇ m or less.
- the “average thickness” refers to a value obtained by dividing the cutout mass in cutout of a substrate having a predetermined area by the true density and cutout area of the substrate. Hereinafter, the same applies to the “average thickness”.
- the intermediate layer is a coating layer on the surface of the positive substrate, and contains conductive particles such as carbon particles to reduce contact resistance between the positive substrate and the positive active material layer.
- the configuration of the intermediate layer is not particularly limited but can be formed of, for example, a composition containing a resin binder and conductive particles.
- the positive active material layer is formed of a so-called positive composite containing a positive active material.
- the positive composite forming the positive active material layer may contain optional components such as a conductive agent, a binder, a thickener, and a filler and the like as necessary.
- the positive active material can be appropriately selected from known positive active materials.
- As the positive active material for a lithium secondary battery a material capable of storing and releasing lithium ions is usually used.
- the positive active material include lithium transition metal composite oxides having an ⁇ -NaFeO 2 -type crystal structure, lithium transition metal oxides having a spinel-type crystal structure, polyanion compounds, chalcogenides, and sulfur.
- lithium transition metal composite oxide having an ⁇ -NaFeO 2 -type crystal structure examples include Li[Li x Ni 1 ⁇ x ]O 2 (0 ⁇ x ⁇ 0.5), Li[Li x Ni ⁇ Co 1 ⁇ x ⁇ ]O 2 (0 ⁇ x ⁇ 0.5, 0 ⁇ 1), Li[Li x Co 1 ⁇ x ]O 2 (0 ⁇ x ⁇ 0.5), Li[Li x Ni ⁇ Mn 1 ⁇ x ⁇ ]O 2 (0 ⁇ x ⁇ 0.5, 0 ⁇ 1), Li[Li x Ni ⁇ Mn ß Co 1 ⁇ x ⁇ ß ]O 2 (0 ⁇ x ⁇ 0.5, 0 ⁇ , 0 ⁇ ß, 0.5 ⁇ +ß ⁇ 1), and Li[Li x Ni ⁇ Co ß Al 1 ⁇ x ⁇ ß ]O 2 (0 ⁇ x ⁇ 0.5, 0 ⁇ , 0 ⁇ ß, 0.5 ⁇ +ß ⁇ 1).
- Examples of the lithium transition metal oxide having a spinel-type crystal structure include Li x Mn 2 O 4 and Li x Ni ⁇ Mn 2 ⁇ O 4 .
- Examples of the polyanion compounds include LiFePO 4 , LiMnPO 4 , LiNiPO 4 , LiCoPO 4 , Li 3 V 2 (PO 4 ) 3 , Li 2 MnSiO 4 , and Li 2 CoPO 4 F.
- Examples of the chalcogenides include titanium disulfide, molybdenum disulfide, and molybdenum dioxide. A part of atoms or polyanions in these materials may be substituted with atoms or anion species composed of other elements. The surfaces of these materials may be coated with other materials. In the positive active material layer, one of these materials may be used singly, or two or more thereof may be used in mixture.
- a lithium transition metal composite oxide is preferable, and a lithium transition metal composite oxide that has an ⁇ -NaFeO 2 -type crystal structure is more preferable.
- the lithium transition metal composite oxide preferably contains nickel or manganese as a transition metal, and more preferably contains both nickel and manganese.
- the lithium transition metal composite oxide may further contain another transition metal such as cobalt.
- the molar ratio (Li/Me) of lithium (Li) to the transition metal (Me) is preferably more than 1, more preferably 1.1 or more, still more preferably 1.2 or more. The use of such a lithium transition metal composite oxide allows an increase in electric capacity.
- the device tends to be used at a high current density, and typically, dendrites are likely to grow. Accordingly, in the case of the nonaqueous electrolyte energy storage device including the positive electrode including the lithium transition metal composite oxide mentioned above, the effect of suppressing any short circuit can be more remarkably enjoyed.
- the upper limit of the molar ratio (Li/Me) of lithium to the transition metal is preferably 1.6, more preferably 1.5.
- lithium transition metal composite oxide that has an ⁇ -NaFeO 2 -type crystal structure
- a compound represented by the following formula (1) is preferable.
- Me is a transition metal containing Ni or Mn. The condition of 0 ⁇ 1 is met.
- Me in the formula (1) preferably contains Ni and Mn.
- Me is preferably composed substantially of two elements of Ni and Mn or three elements of Ni, Mn, and Co. Me may contain other transition metals.
- the lower limit of the molar ratio (Ni/Me) of Ni to Me is preferably 0.1, more preferably 0.2.
- the upper limit of this molar ratio (Ni/Me) is preferably 0.5, more preferably 0.45.
- the molar ratio (Ni/Me) within the above-mentioned range improves the energy density.
- the lower limit of the molar ratio (Mn/Me) of Mn to Me is preferably 0.5, more preferably 0.55.
- the upper limit of this molar ratio (Mn/Me) is preferably 0.75, more preferably 0.7.
- the molar ratio (Mn/Me) within the above-mentioned range improves the energy density.
- the upper limit of the molar ratio (Co/Me) of Co to Me is preferably 0.3, more preferably 0.2.
- the molar ratio (Co/Me) or the lower limit of the molar ratio (Co/Me) may be 0.
- the molar ratio (Li/Me) of Li to Me is preferably more than 1.0 ( ⁇ >0), more preferably 1.1 or more, still more preferably 1.2 or more.
- the upper limit of this molar ratio (Li/Me) is preferably 1.6, more preferably 1.5.
- the molar ratio (Li/Me) within the range mentioned above increases the discharge capacity.
- the lower limit of the content of the lithium transition metal composite oxide with respect to the total positive active material is preferably 50% by mass, more preferably 80% by mass, still more preferably 95% by mass.
- the content of the lithium transition metal composite oxide with respect to the total positive active material may be 100% by mass.
- the average particle size of the positive active material is preferably 0.1 ⁇ m or more and 20 ⁇ m or less, for example.
- the average particle size of the positive active material is easily manufactured or handled.
- the average particle size of the positive active material is equal to or less than the above upper limit, the electron conductivity of the positive active material layer is improved.
- the term “average particle size” means a value at which a volume-based integrated distribution calculated in accordance with JIS-Z-8819-2 (2001) is 50% based on a particle size distribution measured by a laser diffraction/scattering method for a diluted solution obtained by diluting particles with a solvent in accordance with JIS-Z-8825 (2013).
- a crusher, a classifier, or the like is used to obtain particles of the positive active material in a predetermined shape.
- a crushing method include a method in which a mortar, a ball mill, a sand mill, a vibratory ball mill, a planetary ball mill, a jet mill, a counter jet mill, a whirling airflow type jet mill, or a sieve or the like is used.
- wet type crushing in the presence of water or an organic solvent such as hexane can also be used.
- a classification method a sieve or a wind force classifier or the like is used based on the necessity both in dry manner and in wet manner.
- the content of the positive active material in the positive active material layer is preferably 70% by mass or more and 98% by mass or less, more preferably 80% by mass or more and 97% by mass or less, further preferably 90% by mass or more and 96% by mass or less.
- the content of the positive active material particles within the range mentioned above allows an increase in the electric capacity of the secondary battery.
- the conductive agent is not particularly limited so long as it is a material having conductivity.
- Examples of such a conductive agent include carbonaceous materials; metals; and conductive ceramics.
- Examples of carbonaceous materials include graphite and carbon black.
- Examples of the type of the carbon black include furnace black, acetylene black, and ketjen black. Among these, carbonaceous materials are preferable from the viewpoint of conductivity and coatability. In particular, acetylene black and ketjen black are preferable.
- Examples of the shape of the conductive agent include a powder shape, a sheet shape, and a fibrous shape.
- the content of the conductive agent in the positive active material layer is preferably 1% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 10% by mass or less.
- binder examples include: thermoplastic resins such as fluororesin (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), polyethylene, polypropylene, and polyimide; elastomers such as ethylene-propylene-diene rubber (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR), and fluororubber; and polysaccharide polymers.
- thermoplastic resins such as fluororesin (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), polyethylene, polypropylene, and polyimide
- elastomers such as ethylene-propylene-diene rubber (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR), and fluororubber
- EPDM ethylene-propylene-diene rubber
- SBR styrene
- the content of the binder in the positive active material layer is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 6% by mass or less.
- the active material can be stably held.
- the thickener examples include polysaccharide polymers such as carboxymethylcellulose (CMC) and methylcellulose.
- CMC carboxymethylcellulose
- the thickener has a functional group that reacts with lithium, it is preferable to deactivate this functional group by methylation and the like in advance.
- the thickener is preferably not contained in the positive active material layer in some cases.
- the filler is not particularly limited.
- the filler include polyolefins such as polypropylene and polyethylene, inorganic oxides such as silicon dioxide, aluminum oxide, titanium dioxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide and aluminosilicate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, carbonates such as calcium carbonate, hardly soluble ionic crystals of calcium fluoride, barium fluoride, barium sulfate and the like, nitrides such as aluminum nitride and silicon nitride, and substances derived from mineral resources, such as talc, montmorillonite, boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, bentonite and mica, and artificial products thereof.
- the filler is preferably not contained in the positive active material layer in some cases.
- the positive active material layer may contain a typical nonmetal element such as B, N, P, F, Cl, Br, or I, a typical metal element such as Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, and Ba or a transition metal element such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Nb, or W as a component other than the positive active material, the conductive agent, the binder, the thickener, and the filler.
- a typical nonmetal element such as B, N, P, F, Cl, Br, or I
- a typical metal element such as Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, and Ba
- a transition metal element such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Nb, or W as a component other than the positive active material, the conductive agent, the binder, the
- the negative electrode has a negative substrate and a negative active material layer disposed directly or via an intermediate layer on the negative substrate.
- the intermediate layer of the negative electrode may have the same configuration as the intermediate layer of the positive electrode.
- the negative substrate may have the same configuration as that of the positive substrate, as the material, metals such as copper, nickel, stainless steel, and nickel-plated steel or alloys thereof are used, and copper or a copper alloy is preferable. That is, the negative substrate is preferably a copper foil. Examples of the copper foil include rolled copper foil, electrolytic copper foil, and the like.
- the average thickness of the negative substrate is preferably 2 ⁇ m or more and 35 ⁇ m or less, more preferably 3 ⁇ m or more and 30 ⁇ m or less, still more preferably 4 ⁇ m or more and 25 ⁇ m or less, particularly preferably 5 ⁇ m or more and 20 ⁇ m or less.
- the average thickness of the negative substrate is within the above-described range, it is possible to enhance the energy density per volume of a secondary battery while increasing the strength of the negative substrate.
- the negative active material layer has a lithium alloy.
- the lithium alloy is a component that functions as a negative active material.
- the lithium alloy contains silver.
- the lower limit of the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass, preferably 5% by mass, more preferably 7% by mass.
- the content of silver with respect to the total content of lithium and silver in the lithium alloy is set to be equal to or more than the above lower limit, thereby further suppressing the dendrite growth, and further suppressing short circuits.
- the upper limit of the content of silver with respect to the total content of lithium and silver in the lithium alloy is 20% by mass, preferably 15% by mass, more preferably 10% by mass.
- the content of silver with respect to the total content of lithium and silver in the lithium alloy is set to be less than or equal to the above upper limit, thereby allowing effects such as an increase in energy density.
- the lithium alloy may contain components other than lithium and silver, but is preferably composed substantially of lithium and silver. It is to be noted that the phrase “the lithium alloy is composed substantially of lithium and silver” means that the lithium alloy contains substantially no components other than lithium and silver, and the content of components other than lithium and silver is preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01 by mass.
- the content of components other than lithium and silver within the range mentioned above allows discharge at a low negative electrode potential that is equivalent to that for metal lithium, and then allows a high energy density to be achieved.
- the content of components other than lithium and silver within the range mentioned above allows, as a result, the content of lithium to be increased, and then allows the electric capacity to be increased.
- the negative active material layer may be a layer composed substantially of only a lithium alloy.
- the content of the lithium alloy in the negative active material layer may be 99% by mass or more, and may be 100% by mass.
- the composition ratio between lithium and silver may be non-uniform for each part of the negative active material layer formed from the lithium alloy.
- the negative active material layer may be formed of multiple layers that differ in composition ratio between lithium and silver, and in this case, may include a layer that does not contain one of lithium and silver.
- the negative active material layer may be a single layer formed from a lithium alloy that has a substantially uniform composition ratio between lithium and silver.
- the negative active material layer may be a lithium alloy foil.
- the average thickness of the negative active material layer is preferably 5 ⁇ m or more and 1,000 ⁇ m or less, more preferably 10 ⁇ m or more and 500 ⁇ m or less, still more preferably 30 ⁇ m or more and 300 ⁇ m or less.
- the separator can be appropriately selected from known separators.
- a separator composed of only a substrate layer a separator in which a heat resistant layer containing heat resistant particles and a binder is formed on one surface or both surfaces of the substrate layer, or the like can be used.
- the form of the substrate layer of the separator include a woven fabric, a nonwoven fabric, and a porous resin film. Among these forms, a porous resin film is preferable from the viewpoint of strength, and a nonwoven fabric is preferable from the viewpoint of liquid retaining property of the nonaqueous electrolyte.
- a polyolefin such as polyethylene or polypropylene is preferable from the viewpoint of a shutdown function, and polyimide, aramid or the like is preferable from the viewpoint of resistance to oxidation and decomposition.
- a material obtained by combining these resins may be used.
- the heat resistant particles included in the heat resistant layer preferably have a mass loss of 5% or less in the case of heating from room temperature to 500° C. under the atmosphere, and more preferably have a mass loss of 5% or less in the case of heating from room temperature to 800° C. under the atmosphere.
- Inorganic compounds can be mentioned as materials whose mass loss is less than or equal to a predetermined value when the materials are heated.
- the inorganic compound examples include oxides such as iron oxide, silicon oxide, aluminum oxide, titanium dioxide, barium titanate, zirconium oxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide and aluminosilicate; hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide; nitrides such as aluminum nitride and silicon nitride; carbonates such as calcium carbonate; sulfates such as barium sulfate; hardly soluble ionic crystals of calcium fluoride, barium fluoride, and the like; covalently bonded crystals such as silicon and diamond; and substances derived from mineral resources, such as talc, montmorillonite, boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, bentonite and mica, and artificial products thereof.
- oxides such as iron oxide, silicon oxide, aluminum oxide, titanium dioxide, barium titanate, zirconium
- the inorganic compound a simple substance or a complex of these substances may be used singly, or two or more thereof may be used in mixture.
- silicon oxide, aluminum oxide, or aluminosilicate is preferable from the viewpoint of safety of the energy storage device.
- a porosity of the separator is preferably 80% by volume or less from the viewpoint of strength, and is preferably 20% by volume or more from the viewpoint of discharge performance.
- the “porosity” is a volume-based value, and means a value measured with a mercury porosimeter.
- a polymer gel composed of a polymer and a nonaqueous electrolyte may be used.
- the polymer include polyacrylonitrile, polyethylene oxide, polypropylene oxide, polymethyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, and polyvinylidene fluoride.
- the use of polymer gel has the effect of suppressing liquid leakage.
- a polymer gel may be used in combination with a porous resin film, a nonwoven fabric, or the like as described above.
- the nonaqueous electrolyte includes a fluorinated solvent and/or a lithium salt containing fluorine as an electrolyte salt.
- the nonaqueous electrolyte may be a nonaqueous electrolyte solution that includes: a nonaqueous solvent including a fluorinated solvent; and an electrolyte salt dissolved in the nonaqueous solvent.
- the nonaqueous electrolyte may be a nonaqueous electrolyte solution that includes: a nonaqueous solvent; and an electrolyte salt including a lithium salt containing fluorine, dissolved in the nonaqueous solvent.
- the fluorinated solvent is a solvent that has a fluorine atom.
- the fluorinated solvent may be a solvent in which some or all of hydrogen atoms in a hydrocarbon group in a nonaqueous solvent having the hydrocarbon group are substituted with fluorine atoms.
- the use of the fluorinated solvent allows a film containing LiF, capable of suppressing the dendrite growth, to be formed on the surface of the negative electrode.
- the use of the fluorinated solvent enhances the oxidation resistance, and allows favorable charge-discharge cycle performance to be maintained even in the case of charge in which the positive electrode potential during normal usage reaches a high potential.
- fluorinated solvent examples include fluorinated carbonates, fluorinated carboxylic acid esters, fluorinated phosphoric acid esters, and fluorinated ethers.
- fluorinated carbonates examples include fluorinated carbonates, fluorinated carboxylic acid esters, fluorinated phosphoric acid esters, and fluorinated ethers.
- fluorinated solvents or two or more thereof can be used.
- fluorinated solvents fluorinated carbonates are preferable, and fluorinated cyclic carbonates and fluorinated chain carbonates are more preferably used in combination.
- the use of the cyclic carbonate allows the dissociation of the electrolyte salt to be promoted to improve the ionic conductivity of the nonaqueous electrolyte.
- the uses of the fluorinated chain carbonate allows the viscosity of the nonaqueous electrolyte to be kept low.
- the volume ratio of the fluorinated cyclic carbonate to the fluorinated chain carbonate is preferably in a range from 5:95 to 50:50, for example.
- the lower limit of the content ratio of the fluorinated carbonate in the fluorinated solvent is preferably 50% by volume, more preferably 70% by volume, still more preferably 90% by volume.
- the upper limit of the content ratio of the fluorinated carbonate in the fluorinated solvent may be 100% by volume.
- fluorinated cyclic carbonate examples include fluorinated ethylene carbonates such as fluoroethylene carbonate (FEC) and difluoroethylene carbonate, fluorinated propylene carbonates, and fluorinated butylene carbonates.
- FEC fluoroethylene carbonate
- difluoroethylene carbonate fluorinated propylene carbonates
- fluorinated butylene carbonates fluorinated butylene carbonates.
- fluorinated ethylene carbonates are preferable, and FEC is more preferable.
- the FEC exhibits high oxidation resistance and has a high effect of suppressing side reactions (oxidative decomposition of nonaqueous solvent and the like) that may occur at the time of charge-discharge of the secondary battery.
- fluorinated chain carbonate examples include 2,2,2-trifluoroethyl methyl carbonate and bis(2,2,2-trifluoroethyl)carbonate.
- fluorinated carboxylic acid ester examples include methyl 3,3,3-trifluoropropionate and 2,2,2-trifluoroethyl acetate.
- fluorinated phosphoric acid ester examples include tris(2,2-difluoroethyl) phosphate and tris(2,2,2-trifluoroethyl) phosphate.
- fluorinated ether examples include 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, methylheptafluoropropyl ether, and methylnonafluorobutyl ether.
- the nonaqueous solvent may contain a nonaqueous solvent other than the fluorinated solvent.
- a nonaqueous solvent include carbonates other than the fluorinated solvent, carboxylic acid esters, phosphoric acid esters, ethers, amides, and nitriles.
- the lower limit of the content ratio of the fluorinated solvent to the total nonaqueous solvent is preferably 50% by volume, more preferably 70% by volume, still more preferably 90% by volume, still more preferably 99% by volume.
- the content ratio of the fluorinated solvent to the total nonaqueous solvent is particularly preferably 100% by volume.
- the nonaqueous solvent is composed substantially of only the fluorinated solvent, thereby allowing the oxidation resistance to be further improved.
- lithium salt containing fluorine examples include inorganic lithium salts containing fluorine, such as LiPF 6 , LiPO 2 F 2 , LiBF 4 , and LiN(SO 2 F) 2 , and lithium salts having a fluorinated hydrocarbon group, such as LiSO 3 CF 3 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 )(SO 2 C 4 F 9 ), LiC(SO 2 CF 3 ) 3 and LiC(SO 2 C 2 F 5 ) 3 .
- an inorganic lithium salt containing fluorine is preferable, and LiPF 6 is more preferable.
- the content of the electrolyte salt containing fluorine in the nonaqueous electrolyte is preferably 0.1 mol/dm 3 or more and 2.5 mol/dm 3 or less, more preferably 0.3 mol/dm 3 or more and 2.0 mol/dm 3 or less, further preferably 0.5 mol/dm 3 or more and 1.7 mol/dm 3 or less, and particularly preferably 0.7 mol/dm 3 or more and 1.5 mol/dm 3 or less.
- the content of the lithium salt containing fluorine within the range mentioned above allows the ionic conductivity of the nonaqueous electrolyte to be increased.
- electrolyte salt other electrolyte salts may be used in combination with the lithium salt containing fluorine.
- the content of the lithium salt containing fluorine with respect to the total electrolyte salt is, however, preferably 90 mol % or more, preferably 99 mol % or more, more preferably substantially 100 mol %.
- the content of the total electrolyte salt in the nonaqueous electrolyte is preferably 0.1 mol/dm 3 or more and 2.5 mol/dm 3 or less, more preferably 0.3 mol/dm 3 or more and 2.0 mol/dm 3 or less, further preferably 0.5 mol/dm 3 or more and 1.7 mol/dm 3 or less, and particularly preferably 0.7 mol/dm 3 or more and 1.5 mol/dm 3 or less.
- the content of the total electrolyte salt within the range mentioned above allows the ionic conductivity of the nonaqueous electrolyte to be increased.
- the nonaqueous electrolyte may contain an additive.
- the additive include aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partly hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, and dibenzofuran; partial halides of the aromatic compounds such as 2-fluorobiphenyl, o-cyclohexylfluorobenzene, and p-cyclohexylfluorobenzene; halogenated anisole compounds such as 2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroanisole, and 3,5-difluoroanisole; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, and cyclohexanedicar
- the content of the additive contained in the nonaqueous electrolyte is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7% by mass or less, further preferably 0.2% by mass or more and 5% by mass or less, and particularly preferably 0.3% by mass or more and 3% by mass or less, with respect to the total nonaqueous electrolyte.
- content of the additive is within the above range, it is possible to improve capacity retention performance or charge-discharge cycle performance after high-temperature storage, and to further improve safety.
- the positive electrode potential at the end-of-charge voltage under normal usage is preferably 4.30 V vs. Li/Li + or more, more preferably 4.35 V vs. Li/Li + or more, and further preferably less than 4.40 V vs. Li/Li + or more in some cases.
- the positive electrode potential at the end-of-charge voltage under normal usage is set to be equal to or more than the above lower limit, thereby allowing the discharge capacity to be increased, and allowing the energy density to be increased.
- the upper limit of the positive electrode potential at the end-of-charge voltage under normal usage of the secondary battery is, for example, 5.0 V vs. Li/Li+, and may be 4.8 V vs. Li/Li + or may be 4.7 V vs. Li/Li+.
- the nonaqueous electrolyte energy storage device can be suitably applied to an application in which charge with a high current density is performed.
- Examples of such an application include a power source for an automobile such as an electric vehicle (EV), a hybrid electric vehicle (HEV), or a plug-in hybrid electric vehicle (PHEV), and a power source for charge with regenerative electric power.
- the shape of the nonaqueous electrolyte energy storage device according to the present embodiment is not particularly limited, and examples thereof include cylindrical batteries, pouched batteries, prismatic batteries, flat batteries, coin batteries and button batteries.
- FIG. 1 shows a nonaqueous electrolyte energy storage device 1 as an example of a prismatic battery.
- FIG. 1 is a view showing an inside of a case in a perspective manner.
- An electrode assembly 2 having a positive electrode and a negative electrode which are wound with a separator interposed therebetween is housed in a prismatic case 3 .
- the positive electrode is electrically connected to a positive electrode terminal 4 through a positive electrode lead 41 .
- the negative electrode is electrically connected to a negative electrode terminal 5 via a negative electrode lead 51 .
- the nonaqueous electrolyte energy storage device can be mounted as an energy storage unit (battery module) configured by assembling a plurality of nonaqueous electrolyte energy storage devices 1 on a power source for automobiles such as electric vehicles (EV), hybrid vehicles (HEV), and plug-in hybrid vehicles (PHEV), a power source for electronic devices such as personal computers and communication terminals, or a power source for power storage, or the like.
- a power source for automobiles such as electric vehicles (EV), hybrid vehicles (HEV), and plug-in hybrid vehicles (PHEV), a power source for electronic devices such as personal computers and communication terminals, or a power source for power storage, or the like.
- the technique according to one embodiment of the present invention may be applied to at least one nonaqueous electrolyte energy storage device included in the energy storage unit.
- FIG. 2 shows an example of an energy storage apparatus 30 formed by assembling energy storage units 20 in each of which two or more electrically connected nonaqueous electrolyte energy storage devices 1 are assembled.
- the energy storage apparatus 30 may include a busbar (not illustrated) for electrically connecting two or more nonaqueous electrolyte energy storage devices 1 and a busbar (not illustrated) for electrically connecting two or more energy storage units 20 .
- the energy storage unit 20 or the energy storage apparatus 30 may include a state monitor (not illustrated) that monitors the state of one or more nonaqueous electrolyte energy storage devices.
- a method for manufacturing the nonaqueous electrolyte energy storage device includes: preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte containing a fluorinated solvent, the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- a method for manufacturing the nonaqueous electrolyte energy storage device includes: preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte including a lithium salt containing fluorine, the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- Preparing the negative electrode including the lithium alloy may be fabricating the negative electrode including the lithium alloy.
- the negative electrode can be fabricated by laminating a negative active material layer containing a lithium alloy directly on a negative substrate or over the substrate with an intermediate layer interposed therebetween, and pressing or the like.
- the negative active material layer containing a lithium alloy may be a lithium alloy foil.
- the specific form and suitable form of the negative electrode to be prepared are the same as the specific form and suitable form of the negative electrode provided in the nonaqueous electrolyte energy storage device according to an embodiment of the present invention.
- Preparing the nonaqueous electrolyte containing the fluorinated solvent may be preparing a nonaqueous electrolyte containing a fluorinated solvent.
- the nonaqueous electrolyte can be prepared by mixing respective components constituting the nonaqueous electrolyte, such as a fluorinated solvent and other components.
- the specific form and suitable form of the nonaqueous electrolyte to be prepared are the same as the specific form and suitable form of the nonaqueous electrolyte provided in the nonaqueous electrolyte energy storage device according to an embodiment of the present invention.
- Preparing the nonaqueous electrolyte including the lithium salt containing fluorine may be preparing a nonaqueous electrolyte including the lithium salt containing fluorine.
- the nonaqueous electrolyte can be prepared by mixing respective components constituting the nonaqueous electrolyte, such as a lithium salt containing fluorine and a nonaqueous solvent.
- the specific form and suitable form of the nonaqueous electrolyte to be prepared are the same as the specific form and suitable form of the nonaqueous electrolyte provided in the nonaqueous electrolyte energy storage device according to an embodiment of the present invention.
- the method for manufacturing the nonaqueous electrolyte energy storage device includes, for example, preparing or fabricating the positive electrode, preparing or fabricating a negative electrode, preparing or fabricating a nonaqueous electrolyte, forming an electrode assembly in which the positive electrode and the negative electrode are alternately superposed by stacking or winding the positive electrode and the negative electrode with a separator interposed between the electrodes, housing the positive electrode and the negative electrode (electrode assembly) in a case, and injecting the nonaqueous electrolyte into the case.
- the nonaqueous electrolyte energy storage device can be obtained by sealing an injection port after the injection.
- nonaqueous electrolyte energy storage device can also be manufactured by irreversibly supplying lithium from the positive electrode at the time of initial charge to adjust the content of silver to be 3% by mass or more and 20% by mass or less with respect to the total content of lithium and silver in the lithium alloy of the negative electrode.
- a configuration according to one embodiment can additionally be provided with a configuration according to another embodiment, or a configuration according to one embodiment can partially be replaced with a configuration according to another embodiment or a well-known technique. Furthermore, a part of the configuration according to one embodiment can be removed. In addition, a well-known technique can be added to the configuration according to one embodiment.
- the energy storage device is used as a nonaqueous electrolyte secondary battery (for example, lithium secondary battery) that can be charged and discharged
- a nonaqueous electrolyte secondary battery for example, lithium secondary battery
- the type, shape, size, capacity, and the like of the energy storage device are arbitrary.
- the nonaqueous electrolyte energy storage device according to the present invention can also be applied to capacitors such as various nonaqueous electrolyte secondary batteries, electric double layer capacitors, and lithium ion capacitors.
- a lithium-transition metal composite oxide which had an ⁇ -NaFeO 2 -type crystal structure and was represented by Li 1+ ⁇ Me 1 ⁇ O 2 (Me was a transition metal), was used.
- a positive electrode paste which contained the positive active material, acetylene black (AB) as a conductive agent, and polyvinylidene fluoride (PVDF) as a binder at a mass ratio of 94:4.5:1.5, was prepared using N-methylpyrrolidone (NMP) as a dispersion medium.
- NMP N-methylpyrrolidone
- the positive electrode paste was applied to one surface of an aluminum foil with an average thickness of 15 ⁇ m as a positive substrate, and dried, and the resultant was pressed and cut to fabricate a positive electrode having a positive active material layer disposed in a rectangular shape having a width of 30 mm and a length of 40 mm.
- a lithium-silver alloy foil (with a silver content of 10% by mass with respect to the total content of lithium and silver) of 100 ⁇ m in average thickness as a negative active material was laminated as a negative active material layer, and pressed and then cut to fabricate a negative electrode with a negative active material layer disposed in a rectangular shape of 32 mm in width and 42 mm in length.
- FEC fluoroethylene carbonate
- TFEMC 2,2,2-trifluoroethylmethyl carbonate
- the positive electrode and the negative electrode were stacked with the separator interposed therebetween, thereby fabricating an electrode assembly.
- the electrode assembly was housed in a case, then the nonaqueous electrolyte was injected into the inside of the case, and then an opening of the case was sealed by heat sealing to obtain a nonaqueous electrolyte energy storage device (secondary battery) according to Example 1 as a pouched cell.
- a nonaqueous electrolyte energy storage device (secondary battery) according to Example 1 as a pouched cell.
- the nonaqueous electrolyte energy storage device was subjected to pressing with a jig.
- the fixing screw of the jig was tightened with a tightening torque of 15 cNm such that the pressure applied to the nonaqueous electrolyte energy storage device was about 0.3 MPa.
- Nonaqueous electrolyte energy storage devices according to Example 2 and Comparative Examples 1 to 11 were obtained similarly to Example 1 except that the type (composition) of the negative active material was employed as presented in Table 1.
- the composition ratio (the content of silver with respect to the total content of lithium and silver) of the lithium alloy used for the fabrication of the negative electrode, subjected to no charge-discharge is substantially the same as the composition ratio of the lithium alloy in a discharged state.
- the obtained respective nonaqueous electrolyte energy storage devices were subjected to the initial charge-discharge under the following conditions.
- constant current constant voltage charge was performed at a charge current of 0.1 C and an end-of-charge voltage of 4.60 V.
- charge was performed until the charge current reached 0.02 C.
- a pause time of 10 minutes was provided.
- constant current discharge was performed at a discharge current of 0.1 C and an end-of-discharge voltage of 2.00 V, and then a pause time of 10 minutes was provided. This charge-discharge cycle was performed for 2 cycles.
- nonaqueous electrolyte energy storage devices were prepared for three samples, and subjected to the charge-discharge cycle test.
- the number of cycles until causing a short circuit shown in Table 1 and FIG. 3 , was considered as an average value for the three samples.
- FIG. 4 shows a graph showing an amount of charge for each cycle in a charge-discharge cycle test for the nonaqueous electrolyte energy storage device according to Example 1.
- FIG. 5 shows the charge-discharge curves of the nonaqueous electrolyte energy storage devices according to Example 1 and Comparative Example 11 in the first cycle.
- Patent Document 1 charge-discharge cycle characteristics based on the number of cycles in which the discharge capacity is reduced to half with respect to the initial discharge capacity are evaluated in Patent Document 1.
- the evaluation is performed based on the number of cycles until causing the first short circuit.
- various factors are involved in the decrease in discharge capacity, and thus, whether the short circuit is suppressed or not can be considered indirectly evaluated in Patent Document 1. From such a viewpoint as well, the result of Patent Document 1 and the result of the example are believed to have different tendencies.
- the increased amount of charge was small even after the short circuit was caused from the 31 to 33 cycles. From the foregoing, the dendrite growth at the short-circuited site is presumed to be suppressed even after the short circuit.
- the oxidation-reduction potential of the alloy itself such as Li 9 Ag or Li 4 Ag appears as a potential that is higher than the oxidation-reduction potential of metal lithium as the content of lithium decreases with discharge.
- a Li 9 Ag alloy or the like is believed to be mixed in a large amount of metal lithium, and actually, only the metal lithium is believed to react mainly, thereby resulting in almost the same voltage as that in the case where the metal lithium alone serves as a negative electrode.
- the electric capacity is lower than that in the case of the metal lithium alone, but in the nonaqueous electrolyte energy storage device according to Example 1, because of the low content of silver, the decrease in electric capacity can be considered also small.
- the present invention can be applied to a nonaqueous electrolyte energy storage device used as a power source for electronic devices such as personal computers and communication terminals, automobiles, and the like.
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Abstract
An aspect of the present invention is a nonaqueous electrolyte energy storage device that includes a negative electrode including a lithium alloy and a nonaqueous electrolyte containing a fluorinated solvent, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less. Another aspect of the present invention is a nonaqueous electrolyte energy storage device that includes a negative electrode including a lithium alloy and a nonaqueous electrolyte including a lithium salt containing fluorine, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
Description
- The present invention relates to a nonaqueous electrolyte energy storage device and a method for manufacturing the same.
- Nonaqueous electrolyte secondary batteries typified by lithium ion secondary batteries are widely used for electronic devices such as personal computers and communication terminals, motor vehicles, and the like since these secondary batteries have a high energy density. The nonaqueous electrolyte secondary batteries generally include a pair of electrodes, which are electrically separated from each other by a separator, and a nonaqueous electrolyte interposed between the electrodes, and are configured to allow ions to be transferred between the two electrodes for charge-discharge. Capacitors such as lithium ion capacitors and electric double-layer capacitors are also widely used as nonaqueous electrolyte energy storage devices other than nonaqueous electrolyte secondary batteries.
- Metal lithium is known as a negative active material with a high energy density for use in nonaqueous electrolyte energy storage devices. However, in a nonaqueous electrolyte energy storage device in which metal lithium is used for a negative active material, metal lithium may be precipitated in a dendritic form at the surface of the negative electrode during charge (hereinafter, metal lithium in a dendritic form is referred to as a “dendrite”). When the dendrite grows, penetrates a separator, and then comes into contact with a positive electrode, a short circuit is caused. For this reason, a nonaqueous electrolyte energy storage device including metal lithium as a negative active material has the disadvantage that a short circuit is likely to be caused by repeating charge-discharge. As a technique for suppressing the growth of the dendrite, the use of a lithium alloy for a negative active material has been proposed (see
Patent Documents 1 to 3). - Specifically,
Patent Document 1 describes the invention of a nonaqueous electrolyte solution secondary battery characterized in that a negative electrode is an alloy in solid solution of; lithium; and a metal capable of dissolution in lithium as a solid solution. In examples ofPatent Document 1, zinc, magnesium, and silver are used as a metal capable of dissolution in lithium as a solid solution, with the result that charge-discharge cycle characteristics are similarly improved in each case of the lithium alloys used. In the examples ofPatent Document 1, a mixed solvent of propylene carbonate and 1,2-dimethoxyethane that are equal in volume is used as a nonaqueous solvent. In addition, in the examples ofPatent Document 1, a nonaqueous electrolyte solution with a lithium perchlorate dissolved in the mixed solvent of propylene carbonate and 1,2-dimethoxyethane that are equal in volume is used as a nonaqueous electrolyte. -
- Patent Document 1: JP-A-5-47381
- Patent Document 2: JP-A-7-22017
- Patent Document 3: JP-A-61-74258
- In nonaqueous electrolyte energy storage devices, the use of fluorinated solvents such as fluorinated carbonates have been studied for purpose such as suppressing the oxidative decomposition of nonaqueous electrolytes, caused under high potentials. The inventors have found, however, that in the case of a nonaqueous electrolyte energy storage device in which a nonaqueous electrolyte containing a fluorinated solvent is used, short circuits may be inadequately suppressed even by simply using, as a negative active material, an alloy of a metal capable of dissolution in lithium as a solid solution and metal lithium as mentioned in
Patent Document 1. - In nonaqueous electrolyte energy storage devices, typically, fluorine-containing lithium salts with favorable oxidation resistance, solubility, dissociability of lithium ions, and the like are often used as the electrolyte salt. The inventors have found, however, that in the case of a nonaqueous electrolyte energy storage device in which a nonaqueous electrolyte including a lithium salt containing fluorine is used, short circuits may be inadequately suppressed even by simply using, as a negative active material, an alloy of a metal capable of dissolution in lithium as a solid solution and metal lithium as mentioned in
Patent Document 1. - The present invention has been made in view of the circumstances as described above.
- An object of the present invention is to provide a nonaqueous electrolyte energy storage device including a nonaqueous electrolyte containing a fluorinated solvent, in which any short circuit is suppressed, and a method for manufacturing such a nonaqueous electrolyte energy storage device.
- Another object of the present invention is to provide a nonaqueous electrolyte energy storage device including a nonaqueous electrolyte including a lithium salt containing fluorine, in which any short circuit is suppressed, and a method for manufacturing such a nonaqueous electrolyte energy storage device.
- An aspect of the present invention is a nonaqueous electrolyte energy storage device that includes a negative electrode including a lithium alloy and a nonaqueous electrolyte containing a fluorinated solvent, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- Another aspect of the present invention is a nonaqueous electrolyte energy storage device that includes a negative electrode including a lithium alloy and a nonaqueous electrolyte including a lithium salt containing fluorine, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- Another aspect of the present invention is a method for manufacturing a nonaqueous electrolyte energy storage device, including: preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte containing a fluorinated solvent, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- Another aspect of the present invention is a method for manufacturing a nonaqueous electrolyte energy storage device, including: preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte including a lithium salt containing fluorine, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- According to an aspect of the present invention, it is possible to provide a nonaqueous electrolyte energy storage device including a nonaqueous electrolyte containing a fluorinated solvent, in which any short circuit is suppressed, and a method for manufacturing such a nonaqueous electrolyte energy storage device.
- According to another aspect of the present invention, it is possible to provide a nonaqueous electrolyte energy storage device including a nonaqueous electrolyte including a lithium salt containing fluorine, in which any short circuit is suppressed, and a method for manufacturing such a nonaqueous electrolyte energy storage device.
-
FIG. 1 is an external perspective view showing a nonaqueous electrolyte energy storage device according to one embodiment of the present invention. -
FIG. 2 is a schematic view illustrating an energy storage apparatus configured by assembling a plurality of the nonaqueous electrolyte energy storage devices according to an embodiment of the present invention. -
FIG. 3 is a graph showing the number of cycles until causing any short circuit in nonaqueous electrolyte energy storage devices according to examples and comparative examples. -
FIG. 4 is a graph showing an amount of charge for each cycle in a charge-discharge cycle test for a nonaqueous electrolyte energy storage device according to Example 1. -
FIG. 5 shows the charge-discharge curves of nonaqueous electrolyte energy storage devices according to Example 1 and Comparative Example 11 in the first cycle. - First, outlines of a nonaqueous electrolyte energy storage device and a method for manufacturing the nonaqueous electrolyte energy storage device disclosed by the present specification will be described.
- A nonaqueous electrolyte energy storage device according to an aspect of the present invention is a nonaqueous electrolyte energy storage device that includes a negative electrode including a lithium alloy and a nonaqueous electrolyte containing a fluorinated solvent, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- The nonaqueous electrolyte energy storage device suppresses, in spite of including the nonaqueous electrolyte containing the fluorinated solvent, a short circuit due to the growth of a dendrite. Although the reason for this is not clear, the following reason is presumed. The paragraphs [0008], [0020], and the like of
Patent Document 1 describes that the solid solution of a metal in lithium changes the crystal structure of the lithium to cause many active sites for precipitation to be present, thereby densely precipitating lithium during charge, and then inhibiting any dendritic growth. Based on such a theory, the same effect is considered also produced without being affected by the type of the metal in the solid solution in lithium and the type of the nonaqueous solvent. In fact, no difference in the effect due to the metal species in the solid solution is found in any example ofPatent Document 1. In contrast, one of other factors that affect the dendrite growth is the presence of a film containing LiF formed on the surface of the negative electrode. This film, which is derived from a fluorinated solvent or the like, acts for inhibiting the dendrite growth, but when a lithium alloy is used for the negative electrode, the film formed on the surface of the negative electrode is considered likely to be inhomogeneous in some cases, depending on the type of the lithium alloy. In such a case, metal lithium is likely to be precipitated on the inhomogeneous part of the film, and thus, depending on charge-discharge conditions or the like, the dendrite growth is presumed to be unlikely to be sufficiently inhibited. In contrast, when the lithium alloy for use in the negative electrode contains silver, and when the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less, possibly because no oxidative-reductive reaction of the silver is substantially developed during charge-discharge, a film derived from the fluorinated solvent or the like, formed on the surface of the negative electrode, is likely to have high homogeneity, and the dendrite growth is presumed to be sufficiently suppressed, thereby making any short circuit unlikely to be caused. In addition, the nonaqueous electrolyte energy storage device according to an aspect of the present invention has a sufficiently high energy density, because the content of silver with respect to the total content of lithium and silver in the lithium alloy is 20% by mass or less, with the high content of lithium. Furthermore, the nonaqueous electrolyte energy storage device, in which the dendrite growth is inhibited, thus allows sufficient discharge with a small decrease in charge-discharge efficiency. - A nonaqueous electrolyte energy storage device according to another aspect of the present invention is a nonaqueous electrolyte energy storage device that includes a negative electrode including a lithium alloy and a nonaqueous electrolyte including a lithium salt containing fluorine, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- The nonaqueous electrolyte energy storage device suppresses, in spite of including the nonaqueous electrolyte including the lithium salt containing fluorine, a short circuit due to the growth of a dendrite. Although the reason for this is not clear, the following reason is presumed. The paragraphs [0008], [0020], and the like of
Patent Document 1 describes that the solid solution of a metal in lithium changes the crystal structure of the lithium to cause many active sites for precipitation to be present, thereby densely precipitating lithium during charge, and then inhibiting any dendritic growth. Based on such a theory, the same effect is considered also produced without being affected by the type of the metal in the solid solution in lithium and the type of the electrolyte salt. In fact, no difference in the effect due to the metal species in the solid solution is found in any example ofPatent Document 1. In contrast, one of other factors that affect the dendrite growth is the presence of a film containing LiF formed on the surface of the negative electrode. This film, which is derived from a lithium salt containing fluorine, or the like, acts for inhibiting the dendrite growth, but when a lithium alloy is used for the negative electrode, the film formed on the surface of the negative electrode is considered likely to be inhomogeneous in some cases, depending on the type of the lithium alloy. In such a case, metal lithium is likely to be precipitated on the inhomogeneous part of the film, and thus, depending on charge-discharge conditions or the like, the dendrite growth is presumed to be unlikely to be sufficiently inhibited. In contrast, when the lithium alloy for use in the negative electrode contains silver, and when the content of silver in the lithium alloy is 3% by mass or more and 20% by mass or less, possibly because no oxidative-reductive reaction of the silver is substantially developed during charge-discharge, a film derived from the lithium salt containing fluorine, or the like, formed on the surface of the negative electrode, is likely to have high homogeneity, and the dendrite growth is presumed to be sufficiently suppressed, thereby making any short circuit unlikely to be caused. In addition, the nonaqueous electrolyte energy storage device according to an aspect of the present invention has a sufficiently high energy density, because the content of silver in the lithium alloy is 20% by mass or less, with the high content of lithium. Furthermore, the nonaqueous electrolyte energy storage device, in which the dendrite growth is inhibited, thus allows sufficient discharge with a small decrease in charge-discharge efficiency. - The composition ratio of atoms constituting the lithium alloy (negative active material) in the negative electrode refers to a composition ratio in the lithium alloy discharged by the following method. First, the nonaqueous electrolyte energy storage device is subjected to constant current charge with a current of 0.05 C until the voltage becomes an end-of-charge voltage under normal usage, so that the energy storage device is brought to a fully charged state. After a 30-minute pause, the nonaqueous electrolyte energy storage device is subjected to constant current discharge with a current of 0.05 C to the lower limit voltage during normal usage. The nonaqueous electrolyte energy storage device is disassembled, and the negative electrode is taken out. The lithium alloy is collected from the taken-out negative electrode.
- It is to be noted the term “under normal usage” means use of the nonaqueous electrolyte energy storage device while employing charge conditions recommended or specified for the nonaqueous electrolyte energy storage device. For example, when a charger for the nonaqueous electrolyte energy storage device is prepared, the term refers to a case of using the nonaqueous electrolyte energy storage device by applying the charger.
- In the nonaqueous electrolyte energy storage device according to one aspect of the present invention, the positive electrode potential at the end-of-charge voltage under normal usage is preferably 4.30 V vs. Li/Li+ or higher. When the positive electrode potential at the end-of-charge voltage under normal usage is 4.30 V vs. Li/Li+ or higher, the nonaqueous electrolyte tends to be easily oxidatively decomposed, and the need for the use of a fluorinated solvent and/or a lithium salt containing fluorine is increased, thus increasing the usefulness of the present invention. In addition, when the positive electrode potential at the end-of-charge voltage under normal usage is 4.30 V vs. Li/Li+ or higher, a nonaqueous electrolyte energy storage device with a high energy density can be provided in combination with the use of the lithium alloy as a negative active material.
- The nonaqueous electrolyte energy storage device according to an aspect of the present invention includes a positive electrode including a lithium transition metal composite oxide, in which the lithium transition metal composite oxide preferably has an α-NaFeO2-type crystal structure, contains nickel or manganese as a transition metal, and has a molar ratio (Li/Me) of lithium (Li) to the transition metal (Me) in excess of 1. Such a lithium transition metal composite oxide is a positive active material that is high in electric capacity, and a nonaqueous electrolyte energy storage device including a positive electrode including the oxide is often used at a high current density. Typically, when the current density is high under normal usage of the nonaqueous electrolyte energy storage device, dendrites are likely to grow. Accordingly, in the case of the nonaqueous electrolyte energy storage device including the positive electrode including the lithium transition metal composite oxide mentioned above, the effect of suppressing any short circuit can be more remarkably enjoyed.
- It is to be noted that the composition ratio of atoms constituting the positive active material refers to a composition ratio in a positive active material subjected to no charge-discharge, or a positive active material completely discharged by the following method. First, the nonaqueous electrolyte energy storage device is subjected to constant current charge with a current of 0.05 C until the voltage becomes an end-of-charge voltage under normal usage, so that the energy storage device is brought to a fully charged state. After a 30-minute pause, the nonaqueous electrolyte energy storage device is subjected to constant current discharge with a current of 0.05 C to the lower limit voltage during normal usage. After the nonaqueous electrolyte energy storage device is disassembled to take out the positive electrode, a test battery using a metal lithium electrode as the counter electrode is assembled, constant current discharge is performed at a current value of 10 mA per 1 g of a positive composite until the positive potential reaches 2.0 V (vs. Li/Li+), and the positive electrode is adjusted to the completely discharged state. The test battery is disassembled, and the positive electrode is taken out. An oxide of the positive active material is collected from the taken-out positive electrode.
- The lithium alloy mentioned above is preferably composed substantially of lithium and silver. Any element other than silver is substantially not contained with respect to metal lithium, thereby allowing discharge at a low negative electrode potential that is equivalent to that for metal lithium, and then allowing a high energy density to be achieved. In addition, when the lithium alloy is composed substantially of lithium and silver, the content ratio of lithium can be increased, and the electric capacity can be increased.
- A method for manufacturing a nonaqueous electrolyte energy storage device according to an aspect of the present invention is a method for manufacturing a nonaqueous electrolyte energy storage device, including: preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte containing a fluorinated solvent, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- The manufacturing method is capable of manufacturing a nonaqueous electrolyte energy storage device including a nonaqueous electrolyte containing a fluorinated solvent, in which a short circuit is suppressed.
- A method for manufacturing a nonaqueous electrolyte energy storage device according to another aspect of the present invention is a method for manufacturing a nonaqueous electrolyte energy storage device, including; preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte including a lithium salt containing fluorine, in which the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- The manufacturing method is capable of manufacturing a nonaqueous electrolyte energy storage device including a nonaqueous electrolyte including a lithium salt containing fluorine, in which a short circuit is suppressed.
- Hereinafter, the nonaqueous electrolyte energy storage device according to an embodiment of the present invention and the method for manufacturing the nonaqueous electrolyte energy storage device will be described in order.
- <Nonaqueous Electrolyte Energy Storage Device>
- The nonaqueous electrolyte energy storage device according to an embodiment of the present invention has a positive electrode, a negative electrode, and a nonaqueous electrolyte. Hereinafter, a nonaqueous electrolyte secondary battery (hereinafter, also simply referred to as a “secondary battery”) will be described as an example of the nonaqueous electrolyte energy storage device. The positive electrode and the negative electrode usually form an electrode assembly in which the positive electrode and the negative electrode are alternately superposed by being stacked or wound with a separator interposed therebetween. The electrode assembly is housed in a case, and the case is filled with the nonaqueous electrolyte. The nonaqueous electrolyte is interposed between the positive electrode and the negative electrode. As the case, a known metal case, a resin case or the like, which is usually used as a case of a secondary battery, can be used.
- (Positive Electrode)
- The positive electrode has a positive substrate and a positive active material layer disposed directly or via an intermediate layer on the positive substrate.
- The positive substrate has conductivity. Having “conductivity” means having a volume resistivity of 107 Ω·cm or less that is measured in accordance with JIS-H-0505 (1975), and the term “non-conductivity” means that the volume resistivity is more than 107 Ω·cm. As the material of the positive substrate, a metal such as aluminum, titanium, tantalum, stainless steel, or an alloy thereof is used. Among these, aluminum and aluminum alloys are preferable from the viewpoint of the balance of electric potential resistance, high conductivity, and cost. Example of the form of formation of the positive substrate include a foil and a vapor deposition film, and a foil is preferred from the viewpoint of cost. In other words, an aluminum foil is preferable as the positive substrate. Examples of the aluminum or aluminum alloy include A1085 and A3003 prescribed in JIS-H-4000 (2014).
- The average thickness of the positive substrate is preferably 3 μm or more and 50 μm or less, more preferably 5 μm or more and 40 μm or less, still more preferably 8 μm or more and 30 μm or less, and particularly preferably 10 μm or more and 25 μm or less. When the average thickness of the positive substrate is within the above-described range, it is possible to enhance the energy density per volume of a secondary battery while increasing the strength of the positive substrate. The “average thickness” refers to a value obtained by dividing the cutout mass in cutout of a substrate having a predetermined area by the true density and cutout area of the substrate. Hereinafter, the same applies to the “average thickness”.
- The intermediate layer is a coating layer on the surface of the positive substrate, and contains conductive particles such as carbon particles to reduce contact resistance between the positive substrate and the positive active material layer. The configuration of the intermediate layer is not particularly limited but can be formed of, for example, a composition containing a resin binder and conductive particles.
- The positive active material layer is formed of a so-called positive composite containing a positive active material. The positive composite forming the positive active material layer may contain optional components such as a conductive agent, a binder, a thickener, and a filler and the like as necessary.
- The positive active material can be appropriately selected from known positive active materials. As the positive active material for a lithium secondary battery, a material capable of storing and releasing lithium ions is usually used. Examples of the positive active material include lithium transition metal composite oxides having an α-NaFeO2-type crystal structure, lithium transition metal oxides having a spinel-type crystal structure, polyanion compounds, chalcogenides, and sulfur. Examples of the lithium transition metal composite oxide having an α-NaFeO2-type crystal structure include Li[LixNi1−x]O2 (0≤x<0.5), Li[LixNiγCo1−x−γ]O2 (0≤x<0.5, 0<γ<1), Li[LixCo1−x]O2 (0≤x<0.5), Li[LixNiγMn1−x−γ]O2 (0≤x<0.5, 0≤γ<1), Li[LixNiγMnßCo1−x−γ−ß]O2 (0≤x<0.5, 0<γ, 0<ß, 0.5<γ+ß<1), and Li[LixNiγCoßAl1−x−γ−ß]O2 (0≤x<0.5, 0<γ, 0<ß, 0.5<γ+ß<1). Examples of the lithium transition metal oxide having a spinel-type crystal structure include LixMn2O4 and LixNiγMn2−γO4. Examples of the polyanion compounds include LiFePO4, LiMnPO4, LiNiPO4, LiCoPO4, Li3V2(PO4)3, Li2MnSiO4, and Li2CoPO4F. Examples of the chalcogenides include titanium disulfide, molybdenum disulfide, and molybdenum dioxide. A part of atoms or polyanions in these materials may be substituted with atoms or anion species composed of other elements. The surfaces of these materials may be coated with other materials. In the positive active material layer, one of these materials may be used singly, or two or more thereof may be used in mixture.
- As the positive active material, a lithium transition metal composite oxide is preferable, and a lithium transition metal composite oxide that has an α-NaFeO2-type crystal structure is more preferable. The lithium transition metal composite oxide preferably contains nickel or manganese as a transition metal, and more preferably contains both nickel and manganese. The lithium transition metal composite oxide may further contain another transition metal such as cobalt. In the lithium transition metal composite oxide that has an α-NaFeO2-type crystal structure, the molar ratio (Li/Me) of lithium (Li) to the transition metal (Me) is preferably more than 1, more preferably 1.1 or more, still more preferably 1.2 or more. The use of such a lithium transition metal composite oxide allows an increase in electric capacity. In addition, in the case of a nonaqueous electrolyte energy storage device with such a positive active material used, the device tends to be used at a high current density, and typically, dendrites are likely to grow. Accordingly, in the case of the nonaqueous electrolyte energy storage device including the positive electrode including the lithium transition metal composite oxide mentioned above, the effect of suppressing any short circuit can be more remarkably enjoyed. It is to be noted that the upper limit of the molar ratio (Li/Me) of lithium to the transition metal is preferably 1.6, more preferably 1.5.
- As the lithium transition metal composite oxide that has an α-NaFeO2-type crystal structure, a compound represented by the following formula (1) is preferable.
-
Li1+αMe1−αO2 (1) - In the formula (1), Me is a transition metal containing Ni or Mn. The condition of 0<α<1 is met.
- Me in the formula (1) preferably contains Ni and Mn. Me is preferably composed substantially of two elements of Ni and Mn or three elements of Ni, Mn, and Co. Me may contain other transition metals.
- In the formula (1), the lower limit of the molar ratio (Ni/Me) of Ni to Me is preferably 0.1, more preferably 0.2. In contrast, the upper limit of this molar ratio (Ni/Me) is preferably 0.5, more preferably 0.45. The molar ratio (Ni/Me) within the above-mentioned range improves the energy density.
- In the formula (1), the lower limit of the molar ratio (Mn/Me) of Mn to Me is preferably 0.5, more preferably 0.55. In contrast, the upper limit of this molar ratio (Mn/Me) is preferably 0.75, more preferably 0.7. The molar ratio (Mn/Me) within the above-mentioned range improves the energy density.
- In the formula (1), the upper limit of the molar ratio (Co/Me) of Co to Me is preferably 0.3, more preferably 0.2. The molar ratio (Co/Me) or the lower limit of the molar ratio (Co/Me) may be 0.
- In the formula (1), the molar ratio (Li/Me) of Li to Me, that is, (1+α)/(1−α) is preferably more than 1.0 (α>0), more preferably 1.1 or more, still more preferably 1.2 or more. In contrast, the upper limit of this molar ratio (Li/Me) is preferably 1.6, more preferably 1.5. The molar ratio (Li/Me) within the range mentioned above increases the discharge capacity.
- The lower limit of the content of the lithium transition metal composite oxide with respect to the total positive active material is preferably 50% by mass, more preferably 80% by mass, still more preferably 95% by mass. The content of the lithium transition metal composite oxide with respect to the total positive active material may be 100% by mass.
- The average particle size of the positive active material is preferably 0.1 μm or more and 20 μm or less, for example. By setting the average particle size of the positive active material to be equal to or greater than the above lower limit, the positive active material is easily manufactured or handled. By setting the average particle size of the positive active material to be equal to or less than the above upper limit, the electron conductivity of the positive active material layer is improved. Here, the term “average particle size” means a value at which a volume-based integrated distribution calculated in accordance with JIS-Z-8819-2 (2001) is 50% based on a particle size distribution measured by a laser diffraction/scattering method for a diluted solution obtained by diluting particles with a solvent in accordance with JIS-Z-8825 (2013).
- A crusher, a classifier, or the like is used to obtain particles of the positive active material in a predetermined shape. Examples of a crushing method include a method in which a mortar, a ball mill, a sand mill, a vibratory ball mill, a planetary ball mill, a jet mill, a counter jet mill, a whirling airflow type jet mill, or a sieve or the like is used. At the time of crushing, wet type crushing in the presence of water or an organic solvent such as hexane can also be used. As a classification method, a sieve or a wind force classifier or the like is used based on the necessity both in dry manner and in wet manner. The content of the positive active material in the positive active material layer is preferably 70% by mass or more and 98% by mass or less, more preferably 80% by mass or more and 97% by mass or less, further preferably 90% by mass or more and 96% by mass or less. The content of the positive active material particles within the range mentioned above allows an increase in the electric capacity of the secondary battery.
- The conductive agent is not particularly limited so long as it is a material having conductivity. Examples of such a conductive agent include carbonaceous materials; metals; and conductive ceramics. Examples of carbonaceous materials include graphite and carbon black. Examples of the type of the carbon black include furnace black, acetylene black, and ketjen black. Among these, carbonaceous materials are preferable from the viewpoint of conductivity and coatability. In particular, acetylene black and ketjen black are preferable. Examples of the shape of the conductive agent include a powder shape, a sheet shape, and a fibrous shape.
- The content of the conductive agent in the positive active material layer is preferably 1% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 10% by mass or less. By setting the content of the conductive agent in the above range, the energy density of the secondary battery can be enhanced.
- Examples of the binder include: thermoplastic resins such as fluororesin (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), polyethylene, polypropylene, and polyimide; elastomers such as ethylene-propylene-diene rubber (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR), and fluororubber; and polysaccharide polymers.
- The content of the binder in the positive active material layer is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 6% by mass or less. When the content of the binder is in the above range, the active material can be stably held.
- Examples of the thickener include polysaccharide polymers such as carboxymethylcellulose (CMC) and methylcellulose. When the thickener has a functional group that reacts with lithium, it is preferable to deactivate this functional group by methylation and the like in advance. According to an aspect of the present invention, the thickener is preferably not contained in the positive active material layer in some cases.
- The filler is not particularly limited. Examples of the filler include polyolefins such as polypropylene and polyethylene, inorganic oxides such as silicon dioxide, aluminum oxide, titanium dioxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide and aluminosilicate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, carbonates such as calcium carbonate, hardly soluble ionic crystals of calcium fluoride, barium fluoride, barium sulfate and the like, nitrides such as aluminum nitride and silicon nitride, and substances derived from mineral resources, such as talc, montmorillonite, boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, bentonite and mica, and artificial products thereof. According to an aspect of the present invention, the filler is preferably not contained in the positive active material layer in some cases.
- The positive active material layer may contain a typical nonmetal element such as B, N, P, F, Cl, Br, or I, a typical metal element such as Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, and Ba or a transition metal element such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Nb, or W as a component other than the positive active material, the conductive agent, the binder, the thickener, and the filler.
- (Negative Electrode)
- The negative electrode has a negative substrate and a negative active material layer disposed directly or via an intermediate layer on the negative substrate. The intermediate layer of the negative electrode may have the same configuration as the intermediate layer of the positive electrode.
- Although the negative substrate may have the same configuration as that of the positive substrate, as the material, metals such as copper, nickel, stainless steel, and nickel-plated steel or alloys thereof are used, and copper or a copper alloy is preferable. That is, the negative substrate is preferably a copper foil. Examples of the copper foil include rolled copper foil, electrolytic copper foil, and the like.
- The average thickness of the negative substrate is preferably 2 μm or more and 35 μm or less, more preferably 3 μm or more and 30 μm or less, still more preferably 4 μm or more and 25 μm or less, particularly preferably 5 μm or more and 20 μm or less. When the average thickness of the negative substrate is within the above-described range, it is possible to enhance the energy density per volume of a secondary battery while increasing the strength of the negative substrate.
- The negative active material layer has a lithium alloy. The lithium alloy is a component that functions as a negative active material.
- The lithium alloy contains silver. The lower limit of the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass, preferably 5% by mass, more preferably 7% by mass. The content of silver with respect to the total content of lithium and silver in the lithium alloy is set to be equal to or more than the above lower limit, thereby further suppressing the dendrite growth, and further suppressing short circuits. In contrast, the upper limit of the content of silver with respect to the total content of lithium and silver in the lithium alloy is 20% by mass, preferably 15% by mass, more preferably 10% by mass. The content of silver with respect to the total content of lithium and silver in the lithium alloy is set to be less than or equal to the above upper limit, thereby allowing effects such as an increase in energy density.
- The lithium alloy may contain components other than lithium and silver, but is preferably composed substantially of lithium and silver. It is to be noted that the phrase “the lithium alloy is composed substantially of lithium and silver” means that the lithium alloy contains substantially no components other than lithium and silver, and the content of components other than lithium and silver is preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01 by mass. The content of components other than lithium and silver within the range mentioned above allows discharge at a low negative electrode potential that is equivalent to that for metal lithium, and then allows a high energy density to be achieved. In addition, the content of components other than lithium and silver within the range mentioned above allows, as a result, the content of lithium to be increased, and then allows the electric capacity to be increased.
- The negative active material layer may be a layer composed substantially of only a lithium alloy. For example, the content of the lithium alloy in the negative active material layer may be 99% by mass or more, and may be 100% by mass. In addition, the composition ratio between lithium and silver may be non-uniform for each part of the negative active material layer formed from the lithium alloy. For example, the negative active material layer may be formed of multiple layers that differ in composition ratio between lithium and silver, and in this case, may include a layer that does not contain one of lithium and silver. The negative active material layer may be a single layer formed from a lithium alloy that has a substantially uniform composition ratio between lithium and silver.
- The negative active material layer may be a lithium alloy foil. The average thickness of the negative active material layer is preferably 5 μm or more and 1,000 μm or less, more preferably 10 μm or more and 500 μm or less, still more preferably 30 μm or more and 300 μm or less.
- (Separator)
- The separator can be appropriately selected from known separators. As the separator, for example, a separator composed of only a substrate layer, a separator in which a heat resistant layer containing heat resistant particles and a binder is formed on one surface or both surfaces of the substrate layer, or the like can be used. Examples of the form of the substrate layer of the separator include a woven fabric, a nonwoven fabric, and a porous resin film. Among these forms, a porous resin film is preferable from the viewpoint of strength, and a nonwoven fabric is preferable from the viewpoint of liquid retaining property of the nonaqueous electrolyte. As the material of the substrate layer of the separator, a polyolefin such as polyethylene or polypropylene is preferable from the viewpoint of a shutdown function, and polyimide, aramid or the like is preferable from the viewpoint of resistance to oxidation and decomposition. As the substrate layer of the separator, a material obtained by combining these resins may be used.
- The heat resistant particles included in the heat resistant layer preferably have a mass loss of 5% or less in the case of heating from room temperature to 500° C. under the atmosphere, and more preferably have a mass loss of 5% or less in the case of heating from room temperature to 800° C. under the atmosphere. Inorganic compounds can be mentioned as materials whose mass loss is less than or equal to a predetermined value when the materials are heated. Examples of the inorganic compound include oxides such as iron oxide, silicon oxide, aluminum oxide, titanium dioxide, barium titanate, zirconium oxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide and aluminosilicate; hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide; nitrides such as aluminum nitride and silicon nitride; carbonates such as calcium carbonate; sulfates such as barium sulfate; hardly soluble ionic crystals of calcium fluoride, barium fluoride, and the like; covalently bonded crystals such as silicon and diamond; and substances derived from mineral resources, such as talc, montmorillonite, boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, bentonite and mica, and artificial products thereof. As the inorganic compound, a simple substance or a complex of these substances may be used singly, or two or more thereof may be used in mixture. Among these inorganic compounds, silicon oxide, aluminum oxide, or aluminosilicate is preferable from the viewpoint of safety of the energy storage device.
- A porosity of the separator is preferably 80% by volume or less from the viewpoint of strength, and is preferably 20% by volume or more from the viewpoint of discharge performance. Here, the “porosity” is a volume-based value, and means a value measured with a mercury porosimeter.
- As the separator, a polymer gel composed of a polymer and a nonaqueous electrolyte may be used. Examples of the polymer include polyacrylonitrile, polyethylene oxide, polypropylene oxide, polymethyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, and polyvinylidene fluoride. The use of polymer gel has the effect of suppressing liquid leakage. As the separator, a polymer gel may be used in combination with a porous resin film, a nonwoven fabric, or the like as described above.
- (Nonaqueous Electrolyte)
- The nonaqueous electrolyte includes a fluorinated solvent and/or a lithium salt containing fluorine as an electrolyte salt. The nonaqueous electrolyte may be a nonaqueous electrolyte solution that includes: a nonaqueous solvent including a fluorinated solvent; and an electrolyte salt dissolved in the nonaqueous solvent. The nonaqueous electrolyte may be a nonaqueous electrolyte solution that includes: a nonaqueous solvent; and an electrolyte salt including a lithium salt containing fluorine, dissolved in the nonaqueous solvent.
- The fluorinated solvent is a solvent that has a fluorine atom. The fluorinated solvent may be a solvent in which some or all of hydrogen atoms in a hydrocarbon group in a nonaqueous solvent having the hydrocarbon group are substituted with fluorine atoms. The use of the fluorinated solvent allows a film containing LiF, capable of suppressing the dendrite growth, to be formed on the surface of the negative electrode. In addition, the use of the fluorinated solvent enhances the oxidation resistance, and allows favorable charge-discharge cycle performance to be maintained even in the case of charge in which the positive electrode potential during normal usage reaches a high potential. Examples of the fluorinated solvent include fluorinated carbonates, fluorinated carboxylic acid esters, fluorinated phosphoric acid esters, and fluorinated ethers. One of the fluorinated solvents, or two or more thereof can be used.
- Among fluorinated solvents, fluorinated carbonates are preferable, and fluorinated cyclic carbonates and fluorinated chain carbonates are more preferably used in combination. The use of the cyclic carbonate allows the dissociation of the electrolyte salt to be promoted to improve the ionic conductivity of the nonaqueous electrolyte. The uses of the fluorinated chain carbonate allows the viscosity of the nonaqueous electrolyte to be kept low. When the fluorinated cyclic carbonate and the fluorinated chain carbonate are used in combination, the volume ratio of the fluorinated cyclic carbonate to the fluorinated chain carbonate (fluorinated cyclic carbonate fluorinated chain carbonate) is preferably in a range from 5:95 to 50:50, for example.
- The lower limit of the content ratio of the fluorinated carbonate in the fluorinated solvent is preferably 50% by volume, more preferably 70% by volume, still more preferably 90% by volume. The upper limit of the content ratio of the fluorinated carbonate in the fluorinated solvent may be 100% by volume.
- Examples of the fluorinated cyclic carbonate include fluorinated ethylene carbonates such as fluoroethylene carbonate (FEC) and difluoroethylene carbonate, fluorinated propylene carbonates, and fluorinated butylene carbonates. Among these carbonates, fluorinated ethylene carbonates are preferable, and FEC is more preferable. The FEC exhibits high oxidation resistance and has a high effect of suppressing side reactions (oxidative decomposition of nonaqueous solvent and the like) that may occur at the time of charge-discharge of the secondary battery.
- Examples of the fluorinated chain carbonate include 2,2,2-trifluoroethyl methyl carbonate and bis(2,2,2-trifluoroethyl)carbonate.
- Examples of the fluorinated carboxylic acid ester include
methyl - Examples of the fluorinated phosphoric acid ester include tris(2,2-difluoroethyl) phosphate and tris(2,2,2-trifluoroethyl) phosphate.
- Examples of the fluorinated ether include 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, methylheptafluoropropyl ether, and methylnonafluorobutyl ether.
- The nonaqueous solvent may contain a nonaqueous solvent other than the fluorinated solvent. Examples of such a nonaqueous solvent include carbonates other than the fluorinated solvent, carboxylic acid esters, phosphoric acid esters, ethers, amides, and nitriles.
- The lower limit of the content ratio of the fluorinated solvent to the total nonaqueous solvent is preferably 50% by volume, more preferably 70% by volume, still more preferably 90% by volume, still more preferably 99% by volume. The content ratio of the fluorinated solvent to the total nonaqueous solvent is particularly preferably 100% by volume. The nonaqueous solvent is composed substantially of only the fluorinated solvent, thereby allowing the oxidation resistance to be further improved.
- Examples of the lithium salt containing fluorine include inorganic lithium salts containing fluorine, such as LiPF6, LiPO2F2, LiBF4, and LiN(SO2F)2, and lithium salts having a fluorinated hydrocarbon group, such as LiSO3CF3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN(SO2CF3)(SO2C4F9), LiC(SO2CF3)3 and LiC(SO2C2F5)3. Among these salts, an inorganic lithium salt containing fluorine is preferable, and LiPF6 is more preferable.
- The content of the electrolyte salt containing fluorine in the nonaqueous electrolyte is preferably 0.1 mol/dm3 or more and 2.5 mol/dm3 or less, more preferably 0.3 mol/dm3 or more and 2.0 mol/dm3 or less, further preferably 0.5 mol/dm3 or more and 1.7 mol/dm3 or less, and particularly preferably 0.7 mol/dm3 or more and 1.5 mol/dm3 or less. The content of the lithium salt containing fluorine within the range mentioned above allows the ionic conductivity of the nonaqueous electrolyte to be increased.
- As the electrolyte salt, other electrolyte salts may be used in combination with the lithium salt containing fluorine. The content of the lithium salt containing fluorine with respect to the total electrolyte salt is, however, preferably 90 mol % or more, preferably 99 mol % or more, more preferably substantially 100 mol %.
- In the case of using other electrolyte salts in combination with the lithium salt containing fluorine, the content of the total electrolyte salt in the nonaqueous electrolyte is preferably 0.1 mol/dm3 or more and 2.5 mol/dm3 or less, more preferably 0.3 mol/dm3 or more and 2.0 mol/dm3 or less, further preferably 0.5 mol/dm3 or more and 1.7 mol/dm3 or less, and particularly preferably 0.7 mol/dm3 or more and 1.5 mol/dm3 or less. The content of the total electrolyte salt within the range mentioned above allows the ionic conductivity of the nonaqueous electrolyte to be increased.
- The nonaqueous electrolyte may contain an additive. Examples of the additive include aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partly hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, and dibenzofuran; partial halides of the aromatic compounds such as 2-fluorobiphenyl, o-cyclohexylfluorobenzene, and p-cyclohexylfluorobenzene; halogenated anisole compounds such as 2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroanisole, and 3,5-difluoroanisole; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, and cyclohexanedicarboxylic anhydride; ethylene sulfite, propylene sulfite, dimethyl sulfite, dimethyl sulfate, ethylene sulfate, sulfolane, dimethyl sulfone, diethyl sulfone, dimethylsulfoxide, diethyl sulfoxide, tetramethylene sulfoxide, diphenyl sulfide, 4,4′-bis(2,2-dioxo-1,3,2-dioxathiolane), 4-methylsulfonyloxymethyl-2,2-dioxo-1,3,2-dioxathiolane, thioanisole, diphenyl disulfide, dipyridinium disulfide, perfluorooctane, tristrimethylsilyl borate, tristrimethylsilyl phosphate, and tetrakistrimethylsilyl titanate. One of these additives may be used singly, or two or more thereof may be used in mixture.
- The content of the additive contained in the nonaqueous electrolyte is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7% by mass or less, further preferably 0.2% by mass or more and 5% by mass or less, and particularly preferably 0.3% by mass or more and 3% by mass or less, with respect to the total nonaqueous electrolyte. When the content of the additive is within the above range, it is possible to improve capacity retention performance or charge-discharge cycle performance after high-temperature storage, and to further improve safety.
- In the secondary battery (nonaqueous electrolyte energy storage device), the positive electrode potential at the end-of-charge voltage under normal usage is preferably 4.30 V vs. Li/Li+ or more, more preferably 4.35 V vs. Li/Li+ or more, and further preferably less than 4.40 V vs. Li/Li+ or more in some cases. The positive electrode potential at the end-of-charge voltage under normal usage is set to be equal to or more than the above lower limit, thereby allowing the discharge capacity to be increased, and allowing the energy density to be increased.
- The upper limit of the positive electrode potential at the end-of-charge voltage under normal usage of the secondary battery is, for example, 5.0 V vs. Li/Li+, and may be 4.8 V vs. Li/Li+ or may be 4.7 V vs. Li/Li+.
- Dendrites have a tendency to grow when the current density during charge is high. Accordingly, the nonaqueous electrolyte energy storage device according to one embodiment of the present invention can be suitably applied to an application in which charge with a high current density is performed. Examples of such an application include a power source for an automobile such as an electric vehicle (EV), a hybrid electric vehicle (HEV), or a plug-in hybrid electric vehicle (PHEV), and a power source for charge with regenerative electric power.
- The shape of the nonaqueous electrolyte energy storage device according to the present embodiment is not particularly limited, and examples thereof include cylindrical batteries, pouched batteries, prismatic batteries, flat batteries, coin batteries and button batteries.
-
FIG. 1 shows a nonaqueous electrolyteenergy storage device 1 as an example of a prismatic battery.FIG. 1 is a view showing an inside of a case in a perspective manner. Anelectrode assembly 2 having a positive electrode and a negative electrode which are wound with a separator interposed therebetween is housed in aprismatic case 3. The positive electrode is electrically connected to a positive electrode terminal 4 through apositive electrode lead 41. The negative electrode is electrically connected to anegative electrode terminal 5 via anegative electrode lead 51. - <Configuration of Nonaqueous Electrolyte Energy Storage Apparatus>
- The nonaqueous electrolyte energy storage device according to the present embodiment can be mounted as an energy storage unit (battery module) configured by assembling a plurality of nonaqueous electrolyte
energy storage devices 1 on a power source for automobiles such as electric vehicles (EV), hybrid vehicles (HEV), and plug-in hybrid vehicles (PHEV), a power source for electronic devices such as personal computers and communication terminals, or a power source for power storage, or the like. In this case, the technique according to one embodiment of the present invention may be applied to at least one nonaqueous electrolyte energy storage device included in the energy storage unit. -
FIG. 2 shows an example of anenergy storage apparatus 30 formed by assemblingenergy storage units 20 in each of which two or more electrically connected nonaqueous electrolyteenergy storage devices 1 are assembled. Theenergy storage apparatus 30 may include a busbar (not illustrated) for electrically connecting two or more nonaqueous electrolyteenergy storage devices 1 and a busbar (not illustrated) for electrically connecting two or moreenergy storage units 20. Theenergy storage unit 20 or theenergy storage apparatus 30 may include a state monitor (not illustrated) that monitors the state of one or more nonaqueous electrolyte energy storage devices. - <Method for Manufacturing Nonaqueous Electrolyte Energy Storage Device>
- A method for manufacturing the nonaqueous electrolyte energy storage device according to an embodiment of the present invention includes: preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte containing a fluorinated solvent, the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- A method for manufacturing the nonaqueous electrolyte energy storage device according to another embodiment of the present invention includes: preparing a negative electrode including a lithium alloy; and preparing a nonaqueous electrolyte including a lithium salt containing fluorine, the lithium alloy contains silver, and the content of silver with respect to the total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
- Preparing the negative electrode including the lithium alloy may be fabricating the negative electrode including the lithium alloy. The negative electrode can be fabricated by laminating a negative active material layer containing a lithium alloy directly on a negative substrate or over the substrate with an intermediate layer interposed therebetween, and pressing or the like. The negative active material layer containing a lithium alloy may be a lithium alloy foil. The specific form and suitable form of the negative electrode to be prepared are the same as the specific form and suitable form of the negative electrode provided in the nonaqueous electrolyte energy storage device according to an embodiment of the present invention.
- Preparing the nonaqueous electrolyte containing the fluorinated solvent may be preparing a nonaqueous electrolyte containing a fluorinated solvent. The nonaqueous electrolyte can be prepared by mixing respective components constituting the nonaqueous electrolyte, such as a fluorinated solvent and other components. The specific form and suitable form of the nonaqueous electrolyte to be prepared are the same as the specific form and suitable form of the nonaqueous electrolyte provided in the nonaqueous electrolyte energy storage device according to an embodiment of the present invention.
- Preparing the nonaqueous electrolyte including the lithium salt containing fluorine may be preparing a nonaqueous electrolyte including the lithium salt containing fluorine. The nonaqueous electrolyte can be prepared by mixing respective components constituting the nonaqueous electrolyte, such as a lithium salt containing fluorine and a nonaqueous solvent. The specific form and suitable form of the nonaqueous electrolyte to be prepared are the same as the specific form and suitable form of the nonaqueous electrolyte provided in the nonaqueous electrolyte energy storage device according to an embodiment of the present invention.
- The method for manufacturing the nonaqueous electrolyte energy storage device includes, for example, preparing or fabricating the positive electrode, preparing or fabricating a negative electrode, preparing or fabricating a nonaqueous electrolyte, forming an electrode assembly in which the positive electrode and the negative electrode are alternately superposed by stacking or winding the positive electrode and the negative electrode with a separator interposed between the electrodes, housing the positive electrode and the negative electrode (electrode assembly) in a case, and injecting the nonaqueous electrolyte into the case. The nonaqueous electrolyte energy storage device can be obtained by sealing an injection port after the injection.
- In addition, the nonaqueous electrolyte energy storage device according to one embodiment of the present invention can also be manufactured by irreversibly supplying lithium from the positive electrode at the time of initial charge to adjust the content of silver to be 3% by mass or more and 20% by mass or less with respect to the total content of lithium and silver in the lithium alloy of the negative electrode.
- The present invention is not limited to the above embodiments, and various modifications may be made without departing from the gist of the present invention. For example, a configuration according to one embodiment can additionally be provided with a configuration according to another embodiment, or a configuration according to one embodiment can partially be replaced with a configuration according to another embodiment or a well-known technique. Furthermore, a part of the configuration according to one embodiment can be removed. In addition, a well-known technique can be added to the configuration according to one embodiment.
- In the above embodiment, although the case where the energy storage device is used as a nonaqueous electrolyte secondary battery (for example, lithium secondary battery) that can be charged and discharged has been described, the type, shape, size, capacity, and the like of the energy storage device are arbitrary. The nonaqueous electrolyte energy storage device according to the present invention can also be applied to capacitors such as various nonaqueous electrolyte secondary batteries, electric double layer capacitors, and lithium ion capacitors.
- Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
- (Fabrication of Positive Electrode)
- As a positive active material, a lithium-transition metal composite oxide, which had an α-NaFeO2-type crystal structure and was represented by Li1+αMe1−αO2 (Me was a transition metal), was used. In this regard, the molar ratio Li/Me of Li to Me was 1.33, and Me was composed of Ni and Mn and was contained at a molar ratio of Ni:Mn=1:2.
- A positive electrode paste, which contained the positive active material, acetylene black (AB) as a conductive agent, and polyvinylidene fluoride (PVDF) as a binder at a mass ratio of 94:4.5:1.5, was prepared using N-methylpyrrolidone (NMP) as a dispersion medium. The positive electrode paste was applied to one surface of an aluminum foil with an average thickness of 15 μm as a positive substrate, and dried, and the resultant was pressed and cut to fabricate a positive electrode having a positive active material layer disposed in a rectangular shape having a width of 30 mm and a length of 40 mm.
- (Fabrication of Negative Electrode)
- On one surface of a copper foil of 10 μm in average thickness as a negative substrate, a lithium-silver alloy foil (with a silver content of 10% by mass with respect to the total content of lithium and silver) of 100 μm in average thickness as a negative active material was laminated as a negative active material layer, and pressed and then cut to fabricate a negative electrode with a negative active material layer disposed in a rectangular shape of 32 mm in width and 42 mm in length.
- (Preparation of Nonaqueous Electrolyte)
- As a nonaqueous electrolyte, LiPF6 was dissolved at a concentration of 1 mol/dm3 in a mixed solvent of fluoroethylene carbonate (FEC) and 2,2,2-trifluoroethylmethyl carbonate (TFEMC) mixed at a volume ratio of FEC TFEMC=30:70.
- (Fabrication of Nonaqueous Electrolyte Energy Storage Device)
- The positive electrode and the negative electrode were stacked with the separator interposed therebetween, thereby fabricating an electrode assembly. The electrode assembly was housed in a case, then the nonaqueous electrolyte was injected into the inside of the case, and then an opening of the case was sealed by heat sealing to obtain a nonaqueous electrolyte energy storage device (secondary battery) according to Example 1 as a pouched cell. It is to be noted that the nonaqueous electrolyte energy storage device was subjected to pressing with a jig. The fixing screw of the jig was tightened with a tightening torque of 15 cNm such that the pressure applied to the nonaqueous electrolyte energy storage device was about 0.3 MPa.
- Nonaqueous electrolyte energy storage devices according to Example 2 and Comparative Examples 1 to 11 were obtained similarly to Example 1 except that the type (composition) of the negative active material was employed as presented in Table 1.
- It is to be noted that in the nonaqueous electrolyte energy storage devices according to each example and each comparative example, the composition ratio (the content of silver with respect to the total content of lithium and silver) of the lithium alloy used for the fabrication of the negative electrode, subjected to no charge-discharge, is substantially the same as the composition ratio of the lithium alloy in a discharged state.
- (Initial Charge-Discharge)
- The obtained respective nonaqueous electrolyte energy storage devices were subjected to the initial charge-discharge under the following conditions. At 25° C., constant current constant voltage charge was performed at a charge current of 0.1 C and an end-of-charge voltage of 4.60 V. With regard to the charge termination conditions, charge was performed until the charge current reached 0.02 C. Thereafter, a pause time of 10 minutes was provided. Thereafter, constant current discharge was performed at a discharge current of 0.1 C and an end-of-discharge voltage of 2.00 V, and then a pause time of 10 minutes was provided. This charge-discharge cycle was performed for 2 cycles.
- (Charge-Discharge Cycle Test)
- Subsequently, the following charge-discharge cycle test was performed. At 25° C., constant current constant voltage charge was performed at a charge current of 0.2 C and an end-of-charge voltage of 4.60 V. With regard to the charge termination conditions, charge was performed until the charge current reached 0.05 C. Thereafter, a pause time of 10 minutes was provided. Thereafter, constant current discharge was performed at a discharge current of 0.1 C and an end-of-discharge voltage of 2.00 V, and then a pause time of 10 minutes was provided. This charge-discharge cycle was repeated, and the number of cycles was recorded until causing a short circuit. The results are shown in Table 1 and
FIG. 3 . For each example and each comparative example, nonaqueous electrolyte energy storage devices were prepared for three samples, and subjected to the charge-discharge cycle test. The number of cycles until causing a short circuit, shown in Table 1 andFIG. 3 , was considered as an average value for the three samples. -
FIG. 4 shows a graph showing an amount of charge for each cycle in a charge-discharge cycle test for the nonaqueous electrolyte energy storage device according to Example 1.FIG. 5 shows the charge-discharge curves of the nonaqueous electrolyte energy storage devices according to Example 1 and Comparative Example 11 in the first cycle. -
TABLE 1 Negative Electrode Material Cycle (Lithium Alloy or Lithium) Number — Content — Example 1 Li— Ag Ag 10 mass % 32.3 Example 2 Ag 5 mass %28.7 Comparative Ag 1 mass % 24.7 Example 1 Comparative Li—In In 10 mass % 26.0 Example 2 Comparative In 5 mass % 26.3 Example 3 Comparative In 1 mass % 27.0 Example 4 Comparative Li— Zn Zn 10 mass % 26.3 Example 5 Comparative Zn 5 mass % 27.3 Example 6 Comparative Zn 1 mass % 26.3 Example 7 Comparative Li— Al Al 10 mass % 26.3 Example 8 Comparative Al 5 mass % 26.0 Example 9 Comparative Al 1 mass % 25.7 Example 10 Comparative Li ( Li 100 mass %)25.7 Example 11 - As shown in Table 1 and
FIG. 3 , in each case of the lithium-indium alloy, the lithium-zinc alloy, and the lithium-aluminum alloy, regardless of the alloy component and content thereof, a short circuit was caused in the same number of cycles as in the case of 100% by mass of metal lithium, and no short-circuit suppression effect was produced. In contrast, in the case of the lithium-silver alloy, it has been successfully confirmed that a remarkable short-circuit suppression effect was produced by increasing the content of silver. This effect is produced only in the case of a lithium-silver alloy, and believed to be produced by a mechanism in which a fluorinated solvent and/or a lithium salt containing fluorine has some sort of influence, which is different from the invention ofPatent Document 1 in which the same effect is produced regardless of the metal species in solid solution described above. - Further, charge-discharge cycle characteristics based on the number of cycles in which the discharge capacity is reduced to half with respect to the initial discharge capacity are evaluated in
Patent Document 1. In contrast, in the present example, assuming that the first short circuit is caused in a cycle in which the amount of charge is clearly increased, the evaluation is performed based on the number of cycles until causing the first short circuit. Besides the short circuit caused, various factors are involved in the decrease in discharge capacity, and thus, whether the short circuit is suppressed or not can be considered indirectly evaluated inPatent Document 1. From such a viewpoint as well, the result ofPatent Document 1 and the result of the example are believed to have different tendencies. More specifically, in order to suppress short circuits and increase the number of cycles until reaching the increased amount of charge, it can be considered necessary (1) to apply a lithium-silver alloy as a negative electrode in a nonaqueous electrolyte energy storage device with a fluorinated solvent used and/or (2) to apply a lithium-silver alloy as a negative electrode in a nonaqueous electrolyte energy storage device with a lithium salt containing fluorine used. - In addition, as shown in
FIG. 4 , in the nonaqueous electrolyte energy storage device according to Example 1, the increased amount of charge was small even after the short circuit was caused from the 31 to 33 cycles. From the foregoing, the dendrite growth at the short-circuited site is presumed to be suppressed even after the short circuit. - Comparing the first-cycle charge-discharge curves of the nonaqueous electrolyte energy storage devices according to Example 1 (lithium-silver alloy:silver content of 10% by mass) and Comparative Example 11 (metal lithium: 100% by mass) in
FIG. 5 shows that the two charge-discharge curves almost coincide with other. More specifically, the nonaqueous electrolyte energy storage device according to Example 1 has a very small decrease in voltage and a very small decrease in electric capacity due to a change in negative electrode potential caused by alloying, and it has been successfully confirmed that the nonaqueous electrolyte energy storage device has a high energy density that is broadly similar to that in the case of using metal lithium. It is to be noted that typically, in the case where a lithium-silver alloy is used for a negative electrode, the oxidation-reduction potential of the alloy itself such as Li9Ag or Li4Ag appears as a potential that is higher than the oxidation-reduction potential of metal lithium as the content of lithium decreases with discharge. In the case where the content of silver in the lithium-silver alloy is low as in the nonaqueous electrolyte energy storage device according to Example 1, however, a Li9Ag alloy or the like is believed to be mixed in a large amount of metal lithium, and actually, only the metal lithium is believed to react mainly, thereby resulting in almost the same voltage as that in the case where the metal lithium alone serves as a negative electrode. In addition, in the case where the metal lithium of the negative electrode contains therein silver, the electric capacity is lower than that in the case of the metal lithium alone, but in the nonaqueous electrolyte energy storage device according to Example 1, because of the low content of silver, the decrease in electric capacity can be considered also small. - The present invention can be applied to a nonaqueous electrolyte energy storage device used as a power source for electronic devices such as personal computers and communication terminals, automobiles, and the like.
-
-
- 1: nonaqueous electrolyte energy storage device
- 2: electrode assembly
- 3: case
- 4: positive electrode terminal
- 41: positive electrode lead
- 5: negative electrode terminal
- 51: negative electrode lead
- 20: energy storage unit
- 30: energy storage apparatus
Claims (10)
1. A nonaqueous electrolyte energy storage device comprising:
a negative electrode comprising a lithium alloy; and
a nonaqueous electrolyte comprising a fluorinated solvent, wherein
the lithium alloy contains silver, and a content of silver with respect to a total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
2. A nonaqueous electrolyte energy storage device comprising:
a negative electrode comprising a lithium alloy; and
a nonaqueous electrolyte comprising a lithium salt containing fluorine, wherein
the lithium alloy contains silver, and a content of silver with respect to a total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
3. The nonaqueous electrolyte energy storage device according to claim 1 , wherein a positive electrode potential at an end-of-charge voltage under normal usage is 4.30 V vs. Li/Li+ or more.
4. The nonaqueous electrolyte energy storage device according to claim 1 , comprising a positive electrode comprising a lithium transition metal composite oxide, wherein the lithium transition metal composite oxide has an α-NaFeO2-type crystal structure, and comprises nickel or manganese as a transition metal, and a molar ratio of lithium to the transition metal is more than 1.
5. The nonaqueous electrolyte energy storage device according to claim 1 , wherein the lithium alloy is composed substantially of lithium and silver.
6. A method for manufacturing a nonaqueous electrolyte energy storage device, the method comprising:
preparing a negative electrode comprising a lithium alloy; and
preparing a nonaqueous electrolyte comprising a fluorinated solvent, wherein
the lithium alloy contains silver, and a content of silver with respect to a total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
7. A method for manufacturing a nonaqueous electrolyte energy storage device, the method comprising:
preparing a negative electrode comprising a lithium alloy; and
preparing a nonaqueous electrolyte comprising a lithium salt containing fluorine, wherein
the lithium alloy contains silver, and a content of silver with respect to a total content of lithium and silver in the lithium alloy is 3% by mass or more and 20% by mass or less.
8. The nonaqueous electrolyte energy storage device according to claim 2 , wherein a positive electrode potential at an end-of-charge voltage under normal usage is 4.30 V vs. Li/Li+ or more.
9. The nonaqueous electrolyte energy storage device according to claim 2 , comprising a positive electrode comprising a lithium transition metal composite oxide, wherein the lithium transition metal composite oxide has an α-NaFeO2-type crystal structure, and comprises nickel or manganese as a transition metal, and a molar ratio of lithium to the transition metal is more than 1.
10. The nonaqueous electrolyte energy storage device according to claim 2 , wherein the lithium alloy is composed substantially of lithium and silver.
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